Metal Complexes

Abstract

The present invention relates to metal complexes and to electronic devices, especially organic electroluminescent devices, comprising these metal complexes, especially as emitters.

Claims

1-18. (canceled)

19. A monometallic metal complex comprising a hexadentate tripodal ligand wherein three bidentate sub-ligands coordinate to a metal and the three bidentate sub-ligands, which are optionally the same or different, are joined via a bridge of formula (1): ##STR01808## wherein the dotted bonds represent the bonds of the three bidentate sub-ligands to this structure; X.sup.1 is the same or different in each instance and is C, which is optionally substituted, or N; X.sup.2 is the same or different in each instance and is C, which is optionally substituted, or N; or two adjacent X.sup.2 groups together are N, which is optionally substituted, O or S, so as to form a five-membered ring; or two adjacent X.sup.2 groups together are C, which is optionally substituted, or N when one of the X.sup.3 groups in the cycle is N, so as to form a five-membered ring; with the proviso that not more than two adjacent X.sup.2 groups in each ring are N; and wherein any substituents optionally define a ring system with one another or with substituents bonded to X.sup.1; X.sup.3 is C in each instance in one cycle or one X.sup.3 group is N and the other X.sup.3 group in the same cycle is C, wherein the X.sup.3 groups in the three cycles are optionally selected independently, with the proviso that two adjacent X.sup.2 groups together are C, which is optionally substituted, or N when one of the X.sup.3 groups in the cycle is N; and wherein the three bidentate ligands, apart from via the bridge of formula (1), are optionally ring-closed by a further bridge to form a cryptate.

20. The metal complex of claim 19, wherein, when X.sup.1 and/or X.sup.2 is a substituted carbon atom and/or when two adjacent X.sup.2 groups are a substituted nitrogen atom or a substituted carbon atom, the substituent is selected from the following substituents R: R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.1 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, NR.sup.1, O, S, or CONR.sup.1, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.2 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F.

21. The metal complex of claim 19, wherein the group of formula (1) is selected from the structures of formulae (2) to (5): ##STR01809## wherein R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.1 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, NR.sup.1, O, S, or CONR.sup.1, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.2 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F.

22. The metal complex of claim 19, wherein X.sup.3 is C and the group of formula (1) is selected from formulae (2a) to (5a): ##STR01810## wherein R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.1 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, NR.sup.1, O, S, or CONR.sup.1, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S (O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.2 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F.

23. The metal complex of claim 19, wherein the bivalent arylene or heteroarylene groups in the unit of formula (1) are the same or different in each instance and are selected from formulae (7) to (31): ##STR01811## ##STR01812## ##STR01813## wherein the dotted bond in each case represents the position of the linkage to the bidentate sub-ligand; * represents the position of the linkage of the unit to the central trivalent aryl or heteroaryl group in formula (1); and R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.1 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, NR.sup.1, O, S, or CONR.sup.1, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.2 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F.

24. The metal complex of claim 19, wherein the group of formula (1) is selected from the groups of formulae (2b) to (5b): ##STR01814## wherein R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.1 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, NR.sup.1, O, S, or CONR.sup.1, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.2 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F.

25. The metal complex of claim 19, wherein the three bidentate sub-ligands are selected identically or two of the bidentate sub-ligands are selected identically and the third bidentate sub-ligand is different from the first two bidentate sub-ligands.

26. The metal complex of claim 19, wherein the metal is selected from the group consisting of aluminium, indium, gallium, and tin, wherein the bidentate sub-ligands are the same or different in each instance and have two nitrogen atoms or two oxygen atoms or one nitrogen atom and one oxygen atom as coordinating atoms, or wherein the metal is selected from the group consisting of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, iron, cobalt, nickel, palladium, platinum, copper, silver and gold, wherein the bidentate sub-ligands are the same or different in each instance and have one carbon atom and one nitrogen atom or two carbon atoms or two nitrogen atoms or two oxygen atoms or one oxygen atom and one nitrogen atom as coordinating atoms.

27. The metal complex of claim 19, wherein the metal is Ir(III) and two of the bidentate sub-ligands each coordinate to the iridium via one carbon atom and one nitrogen atom and the third of the bidentate sub-ligands coordinates to the iridium via one carbon atom and one nitrogen atom or via two nitrogen atoms or via one nitrogen atom and one oxygen atom or via two oxygen atoms.

28. The metal complex of claim 19, wherein at least one of the bidentate sub-ligands is a structure of formulae (L-1), (L-2), (L-3), or (L-4): ##STR01815## wherein the dotted bond represents the bond of the sub-ligand to the bridge of formula (1); CyC is the same or different in each instance and is a substituted or unsubstituted aryl or heteroaryl group which has 5 to 14 aromatic ring atoms and coordinates to the metal via a carbon atom in each case and which is bonded to CyD in (L-1) and (L-2) via a covalent bond and is bonded to a further CyC group in (L-4) via a covalent bond; CyD is the same or different in each instance and is a substituted or unsubstituted heteroaryl group which has 5 to 14 aromatic ring atoms and coordinates to the metal via a nitrogen atom or via a carbene carbon atom and which is bonded to CyC in (L-1) and (L-2) via a covalent bond and is bonded to a further CyD group in (L-3) via a covalent bond; and wherein two or more of the optional substituents together optionally define a ring system.

29. The metal complex of claim 28, wherein CyC is selected from the structures of formulae (CyC-1) to (CyC-19), wherein the CyC group binds in each case at the position signified by # to CyD in (L-1) and (L-2) and to CyC in (L-4) and at the position signified by * to the metal: ##STR01816## ##STR01817## ##STR01818## wherein CyD is selected from formulae (CyD-1) to (CyD-14), wherein the CyD group binds in each case at the position signified by # to CyC in (L-1) and (L-2) and to CyD in (L-3) and at the position signified by * to the metal: ##STR01819## ##STR01820## wherein R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(O)N(R).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R, P(O)(R).sub.2, S(O)R.sup.1, S(O).sub.2R, OSO.sub.2R, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, NR, O, S, or CONR.sup.1, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.2 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; X is the same or different in each instance and is CR or N, with the proviso that not more than two X per cycle are N; and W is the same or different in each instance and is NR, O, or S; with the proviso that, when the bridge of formula (1) is bonded to CyC, one X is C and the bridge of formula (1) is bonded to this carbon atom and, when the bridge of formula (1) is bonded to CyD, one X is C and the bridge of formula (1) is bonded to this carbon atom.

30. The metal complex of claim 19, wherein at least one of the bidentate sub-ligands is selected from the structures of formulae (L-1-1), (L-1-2), and (L-2-1) to (L-2-3): ##STR01821## wherein X is the same or different in each instance and is CR or N, with the proviso that not more than two X per cycle are N; R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.1 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, NR.sup.1, O, S, or CONR.sup.1, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.2 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; and o represents the position of the bond to the bridge of the formula (1); and/or in that at least one of the bidentate sub-ligands is selected from the structures of formulae (L-5) to (L-32): ##STR01822## ##STR01823## ##STR01824## ##STR01825## ##STR01826## wherein X is the same or different in each instance and is CR or N, with the proviso that not more than two X per cycle are N; R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sup.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.1 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, NR.sup.1, O, S, or CONR.sup.1, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.2 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; * represents the position of coordination to the metal; and o indicates the position at which this sub-ligand is joined to the group of the formula (1); and/or wherein at least one of the bidentate sub-ligands is selected from the structures of formulae (L-33) and (L-34): ##STR01827## wherein R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.1 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, NR.sup.1, O, S, or CONR.sup.1, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.2 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; * represents the position of coordination to the metal; O represents the position of linkage of the sub-ligand to the group of the formula (1); and X is the same or different at each instance and is CR or N, with the proviso that not more than one X symbol per cycle is N; and/or wherein at least one of the bidentate sub-ligands is selected from the structures of formulae (L-41) to (L-44): ##STR01828## wherein the sub-ligands (L-41) to (L-43) each coordinate to the metal via the nitrogen atom explicitly shown and the negatively charged oxygen atom, and the sub-ligand (L-44) coordinates via the two oxygen atoms; X is the same or different in each instance and is CR or N, with the proviso that not more than two X per cycle are N; R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.1 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, NR.sup.1, O, S, or CONR.sup.1, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.2 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F and o indicates the position via which the sub-ligand is joined to the group of the formula (1).

31. The metal complex of claim 19, wherein the metal complex has two R substituents and/or two R.sup.1 substituents which are bonded to adjacent carbon atoms and together define a ring of formulae (43) to (49): ##STR01829## wherein R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R.sup.2 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F the dotted bonds signify the linkage of the two carbon atoms in the ligand and, in addition: A.sup.1 and A.sup.3 are the same or different in each instance and is C(R.sup.3).sub.2, O, S, NR.sup.3, or C(O); A.sup.2 is C(R.sup.1).sub.2, O, S, NR.sup.3, or C(O); G is an alkylene group which has 1, 2, or 3 carbon atoms and is optionally substituted by one or more R.sup.2 radicals, CR.sup.2CR.sup.2, or an ortho-bonded arylene or heteroarylene group which has 5 to 14 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; R.sup.3 is the same or different in each instance and is H, F, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, wherein the alkyl or alkoxy group is optionally substituted in each case by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2, an aromatic or heteroaromatic ring system which has 5 to 24 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 24 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two R.sup.3 radicals bonded to the same carbon atom together optionally define an aliphatic or aromatic ring system to form a spiro system; and wherein R.sup.3 with an adjacent R or R.sup.1 radical optionally defines an aliphatic ring system; with the proviso that no two heteroatoms in these groups are bonded directly to one another and no two CO groups are bonded directly to one another.

32. An oligomer, polymer, or dendrimer containing one or more metal complexes of claim 19, wherein, rather than a hydrogen atom or a substituent, one or more bonds of the metal complex to the polymer, oligomer, or dendrimer are present.

33. A formulation comprising at least one metal complex of claim 19 and at least one solvent.

34. A formulation comprising at least one oligomer, polymer, or dendrimer of claim 32 and at least one solvent.

35. An electronic device comprising at least one metal complex of claim 19.

36. The electronic device of claim 35, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, oxygen sensors, oxygen sensitizers, and organic laser diodes.

37. An electronic device comprising at least one oligomer, polymer, or dendrimer of claim 32.

38. The electronic device of claim 37, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, oxygen sensors, oxygen sensitizers, and organic laser diodes.

39. The electronic device of claim 35, wherein the electronic device is an organic electroluminescent device, wherein the at least one metal complex is used as emitting compound in one or more emitting layers or as hole transport compound in a hole injection or hole transport layer or as electron transport compound in an electron transport or hole blocking layer.

Description

EXAMPLES

[0246] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature.

A: Synthesis of the Synthons SPart 1

Example S1: 4,4,5,5-Tetramethyl-2-(1,1,3,3-tetramethylindan-5-yl)-[1,3,2]dioxaborolane, [1312464-73-5]

[0247] ##STR00549##

[0248] To 800 ml of n-heptane are added 3.3 g (5 mmol) of bis[(1,2,5,6-)-1,5-cyclooctadiene]di--methoxydiiridium(I) [12148-71-9], then 2.7 g (10 mmol) of 4,4-di-tert-butyl-[2,2]bipyridinyl [72914-19-3] and then 5.1 g (10 mmol) of bis(pinacolato)diborane, and the mixture is stirred at room temperature for 15 min. Subsequently, 127.0 g (500 mmol) of bis(pinacolato)diborane [73183-34-3] and then 87.2 g (500 mmol) of 1,1,3,3-tetramethylindane [4834-33-7] are added and the mixture is heated to 80 C. for 12 h (TLC monitoring: heptane:ethyl acetate 5:1). After cooling, 300 ml of ethyl acetate are added to the reaction mixture, which is filtered through a silica gel bed, and the filtrate is concentrated completely under reduced pressure. The crude product is recrystallized twice from acetone (about 800 ml). Yield: 136.6 g (455 mmol), 91%; purity: about 99% by .sup.1H NMR.

[0249] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00009 Product Ex. Reactant Boronic ester Yield S2 [00550] [00551] 87% S3 [00552] [00553] 78% S4 [00554] [00555] 93% S5 [00556] [00557] 90% S6 [00558] [00559] 94%

Example S7: syn,anti-tris-1,3,5-(2-hydroxyphenyl) tris-2,4,6-methylbenzenetristrifluoromethanesulphonate

[0250] ##STR00560##

[0251] To a solution of 11.9 g (30 mmol) of tris-1,3,5-(2-hydroxyphenyl)-tris-2,4,6-methylbenzene (syn-[1421368-51-5] and anti-[1421368-52-6] mixture) in 500 ml of dichloromethane are added, at 5 C., 12.1 ml (150 mmol) of pyridine. Then a mixture of 25.2 ml (150 mmol) of trifluoromethanesulphonic anhydride and 200 ml of dichloromethane is added dropwise over the course of 1 h, and the mixture is stirred at 0 C. for a further 1 h and left to warm up to room temperature while stirring overnight. The reaction mixture is washed cautiously twice with 500 ml each time of 1 N HCl, once with 500 ml of water and once with 500 ml of saturated sodium chloride solution, and then dried over sodium sulphate. The crude product obtained after the dichloromethane has been drawn off is converted further without further purification. Yield: 22.1 g (28 mmol), 93%. Purity: about 95% by .sup.1H NMR, syn/anti mixture.

Example S8: 10-Bromo-6-tert-butylbenzo[4,5]imidazo[1,2-c]quinazoline

[0252] ##STR00561##

[0253] A mixture of 28.8 g (100 mmol) of 2-[5-bromo-1H-benzimidazol-2-yl]phenylamine [1178172-85-4], 42.2 g (350 mmol) of pivaloyl chloride and 30.6 g (300 mmol) of pivalic acid is heated under reflux for 50 h. The reaction mixture is allowed to cool down to about 60 C., 100 ml of ethanol are added, the mixture thus obtained is stirred into a mixture of 500 g of ice and 500 ml of conc. ammonia and stirred for a further 15 min, then the precipitated solid is filtered off with suction, washed twice with 100 ml each time of water and sucked dry. The crude product is taken up in 200 ml of dichloromethane, filtered through a short silica gel column and washed with 200 ml of dichloromethane, and the dichloromethane is removed under reduced pressure. The crude product is chromatographed on silica gel with n-heptane:ethyl acetate (2:1). Yield: 12.0 g (34 mmol), 34%. Purity: about 97% by .sup.1H NMR.

Example S9: 5-Bromo-1,1,3,3-tetramethyl-2,3-dihydro-1H-3b,7-diazacyclopenta[I]phenanthren-6-one

[0254] ##STR00562##

[0255] To a suspension of 2.9 g (10 mmol) of 1,1,3,3-tetramethyl-2,3-dihydro-1H-3b,7-diazacyclopenta[l]phenanthren-6-one [1616465-59-8] in 50 ml of glacial acetic acid is added dropwise at room temperature a solution of 615 l (12 mmol) of bromine in 10 ml of glacial acetic acid. After the addition has ended, the mixture is heated to 60 C. for another 5 h, then the glacial acetic acid is substantially removed under reduced pressure. The residue is taken up in 200 ml of ethyl acetate, washed once with 50 ml of saturated sodium carbonate solution, twice with 50 ml each time of water and once with 50 ml of saturated sodium chloride solution, and dried over magnesium sulphate. The crude product is chromatographed on silica gel with n-heptane:ethyl acetate (2:1). Yield: 2.4 g (6.5 mmol), 65%. Purity: about 97% by .sup.1H NMR.

Example S10: 5-Bromo-2-[1,1,2,2,3,3-hexamethylindan-5-yl]pyridine

[0256] ##STR00563##

[0257] A mixture of 164.2 g (500 mmol) of 2-(1,1,2,2,3,3-hexamethylindan-5-yl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane [152418-16-9] (it is analogously possible to use boronic acids), 142.0 g (500 mmol) of 5-bromo-2-iodopyridine [223463-13-6], 159.0 g (1.5 mol) of sodium carbonate, 5.8 g (5 mmol) of tetrakis(triphenylphosphino)palladium(0), 700 ml of toluene, 300 ml of ethanol and 700 ml of water is heated under reflux with good stirring for 16 h. After cooling, 1000 ml of toluene are added, the organic phase is removed and the aqueous phase is re-extracted with 300 ml of toluene. The combined organic phases are washed once with 500 ml of saturated sodium chloride solution. After the organic phase has been dried over sodium sulphate and the solvent has been removed under reduced pressure, the crude product is recrystallized twice from about 300 ml of EtOH. Yield: 130.8 g (365 mmol), 73%. Purity: about 95% by .sup.1H NMR.

[0258] It is analogously possible to prepare the following compounds, generally using 5-bromo-2-iodopyridine ([223463-13-6]) as pyridine derivative, which is not listed separately in the table which follows, and only different pyridine derivatives are listed explicitly in the table:

TABLE-US-00010 Boronic acid/ester Ex. Pyridine Product Yield S11 [00564] [00565] 76% S12 [00566] [00567] 75% S13 [00568] [00569] 69% S14 [00570] [00571] 71% S15 [00572] [00573] 80% S16 [00574] [00575] 78% S17 [00576] [00577] 78% S18 [00578] [00579] 81% S19 [00580] [00581] 77% S20 [00582] [00583] 73% S59 [00584] [00585] 68% S71 [00586] [00587] 70% S72 [00588] [00589] 65% S73 [00590] [00591] 60% S74 [00592] [00593] 71% S75 [00594] [00595] 69% S76 [00596] [00597] 67% S77 [00598] [00599] 62% S78 [00600] [00601] 48% S79 [00602] [00603] 67% S80 [00604] [00605] 60% S81 [00606] [00607] 65% S82 [00608] [00609] 63% S94 [00610] [00611] 43% S108 [00612] [00613] 76% S125 [00614] [00615] 61% S126 [00616] [00617] 58% S140 [00618] [00619] 53% S141 [00620] [00621] 58% S144 [00622] [00623] 48% S145 [00624] [00625] 39% S146 [00626] [00627] 65% S147 [00628] [00629] 57% S148 [00630] [00631] 81% S149 [00632] [00633] 78% S150 [00634] [00635] 68% S151 [00636] [00637] 24%

Example S21: 2-[1,1,2,2,3,3-Hexamethylindan-5-yl]-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)pyridine

[0259] Variant A:

##STR00638##

[0260] A mixture of 35.8 g (100 mmol) of S10, 25.4 g (100 mmol) of bis(pinacolato)diborane [73183-34-3], 49.1 g (500 mmol) of potassium acetate, 1.5 g (2 mmol) of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II) complex with DCM [95464-05-4], 200 g of glass beads (diameter 3 mm), 700 ml of 1,4-dioxane and 700 ml of toluene is heated under reflux for 16 h. After cooling, the suspension is filtered through a Celite bed and the solvent is removed under reduced pressure. The black residue is digested with 1000 ml of hot n-heptane, cyclohexane or toluene and filtered through a Celite bed while still hot, then concentrated to about 200 ml, in the course of which the product begins to crystallize. Alternatively, hot extraction with ethyl acetate is possible. The crystallization is completed in a refrigerator overnight, and the crystals are filtered off and washed with a little n-heptane. A second product fraction can be obtained from the mother liquor. Yield: 31.6 g (78 mmol) 78%. Purity: about 95% by .sup.1H NMR.

[0261] Variant B: Conversion of Aryl Chlorides

[0262] As variant A, except that, rather than 1,1-bis(diphenylphosphino)-ferrocenedichloropalladium(II) complex with DCM, 2 mmol of SPhos [657408-07-6] and 1 mmol of palladium(II) acetate are used.

[0263] In an analogous manner, it is possible to prepare the following compounds, and it is also possible to use cyclohexane, toluene, acetonitrile or mixtures of said solvents for purification rather than n-heptane:

TABLE-US-00011 BromideVariant A Ex. ChlorideVariant B Product Yield S22 [00639] [00640] 85% S23 [00641] [00642] 80% S24 [00643] [00644] 83% S25 [00645] [00646] 74% S26 [00647] [00648] 77% S27 [00649] [00650] 79% S28 [00651] [00652] 67% S29 [00653] [00654] 70% S30 [00655] [00656] 82% S31 [00657] [00658] 80% S32 [00659] [00660] 80% S33 [00661] [00662] 78% S34 [00663] [00664] 74% S35 [00665] [00666] 76% S36 [00667] [00668] 70% S37 [00669] [00670] 68% S38 [00671] [00672] 76% S39 [00673] [00674] 83% S40 [00675] [00676] 85% S41 [00677] [00678] 80% S42 [00679] [00680] 78% S43 [00681] [00682] 76% S54 [00683] [00684] 72% S55 [00685] [00686] 69% S56 [00687] [00688] 54% S57 [00689] [00690] 41% S58 [00691] [00692] 58% S60 [00693] [00694] 60% S61 [00695] [00696] 66% S62 [00697] [00698] 33% S83 [00699] [00700] 81% S84 [00701] [00702] 77% S85 [00703] [00704] 75% S86 [00705] [00706] 78% S87 [00707] [00708] 70% S88 [00709] [00710] 74% S89 [00711] [00712] 69% S90 [00713] [00714] 73% S91 [00715] [00716] 69% S92 [00717] [00718] 76% S93 [00719] [00720] 75% S95 [00721] [00722] 67% S96 [00723] [00724] 63% S97 [00725] [00726] 48% S98 [00727] [00728] 46% S99 [00729] [00730] 51% S100 [00731] [00732] 48% S103 [00733] [00734] 88% S109 [00735] [00736] 90% S127 [00737] [00738] 87% S128 [00739] [00740] 66% S129 [00741] [00742] 72% S130 [00743] [00744] 75% S131 [00745] [00746] 78% S132 [00747] [00748] 82% S133 [00749] [00750] 80% S134 [00751] [00752] 75% S135 [00753] [00754] 68% S136 [00755] [00756] 80% S137 [00757] [00758] 79% S138 [00759] [00760] 71% S139 [00761] [00762] 76% S142 [00763] [00764] 81% S143 [00765] [00766] 79% S152 [00767] [00768] 76% S153 [00769] [00770] 70% S154 [00771] [00772] 81% S155 [00773] [00774] 84% S156 [00775] [00776] 91% S157 [00777] [00778] 89% S158 [00779] [00780] 90% S159 [00781] [00782] 66%

Example S44: 1,3,5-Tris(6-bromo-1,1,3,3-tetramethylindan-5-yl)benzene

[0264] ##STR00783##

a) 1-(6-Bromo-1,1,3,3-tetramethyl-indan-5-yl)ethanone

[0265] ##STR00784##

[0266] Procedure according to I. Prayst et al., Tetrahedron Lett., 2006, 47, 4707. A mixture of 21.6 g (100 mmol) of 1-(1,1,3,3-tetramethylindan-5-yl)ethanone [17610-14-9], 39.2 g (220 mmol) of N-bromosuccinimide, 1.6 g (2.5 mmol) of [Cp*RhCl.sub.2].sub.2 [12354-85-7], 3.4 g (10 mmol) of silver(I) hexafluoroantimonate [26042-64-8], 20.0 g (110 mmol) of copper(II) acetate [142-71-2] and 500 ml of 1,2-dichloroethane is stirred at 120 C. for 20 h. After cooling, the solids are filtered off using a silica gel bed, the solvent is removed under reduced pressure and the residue is recrystallized three times from acetonitrile. Yield: 12.1 g (41 mmol), 41%. Purity: about 97% by .sup.1H NMR.

b) 1,3,5-Tris(6-bromo-1,1,3,3-tetramethylindan-5-yl)benzene, S44

[0267] A mixture of 12.1 g (41 mmol) of 1-(6-bromo-1,1,3,3-tetramethylindan-5-yl)ethanone and 951 mg (5 mmol) of toluenesulphonic acid monohydrate [6192-52-5] (or trifluoromethanesulphonic acid, Variant B) is stirred on a water separator at 150 C. for 48 h. After cooling, the residue is taken up in 300 ml of ethyl acetate, washed three times with 100 ml each time of water and once with 100 ml of saturated sodium chloride solution, and then dried over magnesium sulphate. The crude product is chromatographed on silica gel with n-heptane:ethyl acetate (5:1). Yield: 4.3 g (5 mmol), 38%. Purity: about 97% by .sup.1H NMR.

[0268] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00012 Ketone or bromoketone Ex. Variant Product Yield S45 [00785] [00786] 52% S46 [00787] [00788] 33% S47 [00789] [00790] 60% S48 [00791] [00792] 23% S49 [00793] [00794] 20%

[0269] The following compounds known from the literature can be used as synthons:

TABLE-US-00013 Synthon [00795] [00796] [00797] [00798] [00799]

Example S102

[0270] ##STR00800##

[0271] A mixture of 54.3 g (100 mmol) of 1,3,5-tris(2-bromophenyl)benzene, S50, [380626-56-2], 80.0 g (315 mmol) of bis(pinacolato)diborane [73183-34-3], 30.9 g (315 mmol) of potassium acetate, 701 mg (2.50 mmol) of tricyclohexylphosphine, 281 mg (1.25 mmol) of palladium(II) acetate, 1000 ml of 1,4-dioxane and 200 g of glass beads (diameter 3 mm) is heated under reflux for 16 h. After cooling, the suspension is filtered through a Celite bed and the solvent is removed under reduced pressure. The residue is taken up in 1000 ml of ethyl acetate, washed three times with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution, and then dried over magnesium sulphate. After the solvent has been removed, the residue is recrystallized from ethyl acetate/methanol. Yield: 56.8 g (83 mmol) 83%. Purity: about 95% by .sup.1H NMR.

[0272] In an analogous manner, it is possible to prepare the following compound:

TABLE-US-00014 Ex. Aryl halide Boronic ester Yield S160 [00801] [00802] 86%

Example S63: 6-(4,4,5,5-Tetramethyl-[1,3,2]dioxaborolan-2-yl]-benzo[4,5]furo[3,2-b]pyridine

[0273] ##STR00803##

[0274] Procedure according to Ishiyama, T. et al., Tetrahedron, 2001, 57(49), 9813.

[0275] To a well-stirred mixture of 20.4 g (100 mmol) of 6-bromobenzo[4,5]furo[3,2-b]pyridine [1609623-76-8], 27.9 g (110 mmol) of bis(pinacolato)diborane [73183-34-3], 19.6 g (200 mmol) of anhydrous potassium acetate and 200 g of glass beads (diameter 3 mm) in 500 ml of dioxane are consecutively added 1.7 g (6 mmol) of tricyclohexylphosphine [2622-14-2] and then 1.7 g (3 mmol) of Pd(dba).sub.2 [32005-36-0], and the mixture is stirred at 90 C. for 16 h. An alternative catalyst system that can be used is 534 mg (1.3 mmol) of SPhos [657408-07-6] and 225 mg (1 mmol) of palladium(II) acetate. After cooling, the solids are filtered off and washed with 200 ml of dioxane, and then the dioxane is substantially removed under reduced pressure. The residue is taken up in 500 ml of ethyl acetate, washed three times with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution, and then dried over magnesium sulphate. The foam obtained after the ethyl acetate has been removed is recrystallized from acetonitrile/methanol.

[0276] Yield: 23.0 g (78 mmol), 78%. Purity: about 95% by .sup.1H NMR.

[0277] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00015 Ex. Aryl halide Boronic ester Yield S64 [00804] [00805] 56% S65 [00806] [00807] 64% S66 [00808] [00809] 76% S67 [00810] [00811] 64% S68 [00812] [00813] 73% S69 [00814] [00815] 70% S70 [00816] [00817] 48% S105 [00818] [00819] 88% S106 [00820] [00821] 76% S107 [00822] [00823] 80% S118 [00824] [00825] 81% S119 [00826] [00827] 78% S120 [00828] [00829] 75% S121 [00830] [00831] 77% S122 [00832] [00833] 70% S123 [00834] [00835] 80% S124 [00836] [00837] 87%

Example S104

[0278] ##STR00838##

[0279] A mixture of 18.1 g (100 mmol) of 6-chlorotetralone [26673-31-4], 16.5 g (300 mmol) of propargylamine [2450-71-7], 796 mg [2 mmol] of sodium tetrachloroaurate(III) dihydrate and 200 ml of ethanol is stirred in an autoclave at 120 C. for 24 h. After cooling, the ethanol is removed under reduced pressure, the residue is taken up in 200 ml of ethyl acetate, the solution is washed three times with 200 ml of water and once with 100 ml of saturated sodium chloride solution and dried over magnesium sulphate, and then the latter is filtered off using a pre-slurried silica gel bed. After the ethyl acetate has been removed under reduced pressure, the residue is chromatographed on silica gel with n-heptane/ethyl acetate (1:2 v/v). Yield: 9.7 g (45 mmol), 45%. Purity: about 98% by .sup.1H NMR.

Example S110

[0280] ##STR00839##

[0281] A mixture of 25.1 g (100 mmol) of 2,5-dibromopyridine [3430-26-0], 15.6 g (100 mmol) of 4-chlorophenylboronic acid [1679-18-1], 27.6 g (200 mmol) of potassium carbonate, 1.57 g (6 mmol) of triphenylphosphine [603-35-0], 676 mg (3 mmol) of palladium(II) acetate [3375-31-3], 200 g of glass beads (diameter 3 mm), 200 ml of acetonitrile and 100 ml of ethanol is heated under reflux for 48 h. After cooling, the solvents are removed under reduced pressure, 500 ml of toluene are added, the mixture is washed twice with 300 ml each time of water and once with 200 ml of saturated sodium chloride solution, dried over magnesium sulphate and filtered through a pre-slurried silica gel bed, which is washed with 300 ml of toluene. After the toluene has been removed under reduced pressure, it is recrystallized once from methanol/ethanol (1:1 v/v) and once from n-heptane. Yield: 17.3 g (61 mmol), 61%. Purity: about 95% by .sup.1H NMR.

Example S111

[0282] ##STR00840##

[0283] A mixture of 28.3 g (100 mmol) of S110, 12.8 g (105 mmol) of phenylboronic acid, 31.8 g (300 mmol) of sodium carbonate, 787 mg (3 mmol) of triphenylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 300 ml of toluene, 150 ml of ethanol and 300 ml of water is heated under reflux for 48 h. After cooling, the mixture is extended with 300 ml of toluene, and the organic phase is removed, washed once with 300 ml of water and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulphate. After the solvent has been removed, the residue is chromatographed on silica gel (toluene/ethyl acetate, 9:1 v/v). Yield: 17.1 g (61 mmol), 61%. Purity: about 97% by .sup.1H NMR.

[0284] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00016 Ex. Boronic ester Product Yield S112 [00841] [00842] 56% S113 [00843] [00844] 61% S114 [00845] [00846] 51% S115 [00847] [00848] 55% S116 [00849] [00850] 61% S117 [00851] [00852] 76%

Example S200

[0285] ##STR00853##

[0286] A mixture of 28.1 g (100 mmol) of 2-phenyl-5-[4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine [879291-27-7], 28.2 g (100 mmol) of 1-bromo-2-iodobenzene [583-55-1], 31.8 g (300 mmol) of sodium carbonate, 787 mg (3 mmol) of triphenylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 300 ml of toluene, 150 ml of ethanol and 300 ml of water is heated under reflux for 24 h. After cooling, the mixture is extended with 500 ml of toluene, and the organic phase is removed, washed once with 500 ml of water and once with 500 ml of saturated sodium chloride solution and dried over magnesium sulphate. After the solvent has been removed, the residue is recrystallized from ethyl acetate/n-heptane or chromatographed on silica gel (toluene/ethyl acetate, 9:1 v/v).

[0287] Yield: 22.7 g (73 mmol), 73%. Purity: about 97% by .sup.1H NMR.

[0288] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00017 Ex. Boronic ester Product Yield S201 [00854] [00855] 56% S202 [00856] [00857] 72% S203 [00858] [00859] 75% S204 [00860] [00861] 71% S205 [00862] [00863] 70% S206 [00864] [00865] 69% S207 [00866] [00867] 67% S208 [00868] [00869] 63% S209 [00870] [00871] 59% S210 [00872] [00873] 48% S211 [00874] [00875] 68% S212 [00876] [00877] 79% S213 [00878] [00879] 70% S214 [00880] [00881] 73% S215 [00882] [00883] 68% S216 [00884] [00885] 65% S217 [00886] [00887] 72% S218 [00888] [00889] 70% S219 [00890] [00891] 55% S220 [00892] [00893] 70% S221 [00894] [00895] 62% S222 [00896] [00897] 48% S223 [00898] [00899] 55% S224 [00900] [00901] 60% S225 [00902] [00903] 64% S226 [00904] [00905] 58%

Example S300

[0289] ##STR00906##

[0290] A mixture of 40.2 g (100 mmol) of 2,2-[5-(trimethylsilyl)-1,3-phenylene]bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolane [383175-93-7], 65.2 g (210 mmol) of S200, 42.4 g (400 mmol) of sodium carbonate, 1.57 g (6 mmol) of triphenylphosphine, 500 mg (2 mmol) of palladium(II) acetate, 500 ml of toluene, 200 ml of ethanol and 500 ml of water is heated under reflux for 48 h. After cooling, the mixture is extended with 500 ml of toluene, and the organic phase is removed, washed once with 500 ml of water and once with 500 ml of saturated sodium chloride solution and dried over magnesium sulphate. After the solvent has been removed, the residue is chromatographed on silica gel (n-heptane/ethyl acetate, 2:1 v/v). Yield: 41.4 g (68 mmol), 68%. Purity: about 95% by .sup.1H NMR.

[0291] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00018 Ex. Bromide Product Yield S301 [00907] [00908] 70% S302 [00909] [00910] 83% S303 [00911] [00912] 72% S304 [00913] [00914] 68% S305 [00915] [00916] 79% S306 [00917] [00918] 80%

Example S400

[0292] ##STR00919##

[0293] To a solution, cooled to 0 C., of 60.9 g (100 mmol) of S300 in 500 ml of dichloromethane is added dropwise, in the dark, a mixture of 8.2 ml (160 mmol) of bromine and 100 ml of dichloromethane. After the addition has ended, the mixture is allowed to warm up to room temperature and stirred for a further 16 h. Then 100 ml of water, 300 ml of sodium hydrogencarbonate solution and then 150 ml of aqueous 5% NaOH solution are added. The organic phase is removed, washed three times with 200 ml of water and once with 200 ml of saturated sodium chloride solution, and then dried over magnesium sulphate. After the solvent has been removed, the oily residue is recrystallized from ethyl acetate (about 1.5 ml/g). Yield: about 20 g of crude product 1. The mother liquor is chromatographed (CombiFlash Torrent from A. Semrau). Yield: about 20 g of crude product 2. The combined crude products together are recrystallized again from ethyl acetate.

[0294] Yield: 33.8 g (55 mmol), 55%. Purity: about 97% by .sup.1H NMR.

[0295] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00019 Ex. Reactant Product Yield S401 [00920] [00921] 48% S402 [00922] [00923] 50% S403 [00924] [00925] 54% S404 [00926] [00927] 55% S405 [00928] [00929] 61%

Example S500

[0296] ##STR00930##

[0297] A mixture of 61.6 g (100 mmol) of S400, 27.9 g (110 mmol) of bis(pinacolato)diborane [73183-34-3], 29.4 g (300 mmol) of potassium acetate, 561 mg (2 mmol) of tricyclohexylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 100 g of glass beads (diameter 3 mm) and 500 ml of 1,4-dioxane is heated under reflux for 16 h. After cooling, the suspension is freed of the 1,4-dioxane under reduced pressure, and the residue is taken up in 500 ml of ethyl acetate, washed twice with 300 ml of water and once with 200 ml of saturated sodium chloride solution, dried over magnesium sulphate and then filtered through a pre-slurried Celite bed, which is washed through with a little ethyl acetate. The filtrate is concentrated to dryness and then recrystallized from ethyl acetate/methanol. Yield: 55.0 g (83 mmol), 83%. Purity: about 97% by .sup.1H NMR.

[0298] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00020 Ex. Reactant Product Yield S501 [00931] [00932] 78% S502 [00933] [00934] 70% S503 [00935] [00936] 64% S504 [00937] [00938] 77% S505 [00939] [00940] 73% S505 [00941] [00942] 80%

Example S600

[0299] ##STR00943##

[0300] A mixture of 66.3 g (100 mmol) of S500, 27.6 g (110 mmol) of 2-bromo-4-fluoro-1,1-biphenyl [89346-54-3], 63.7 g (300 mmol) of tripotassium phosphate, 1.64 g (4 mmol) of SPhos [657408-07-6], 449 mg (2 mmol) of palladium(II) acetate, 700 ml of toluene, 300 ml of dioxane and 500 ml of water is heated under reflux for 8 h. After cooling, the organic phase is removed, washed twice with 300 ml of water and once with 200 ml of saturated sodium chloride solution, dried over magnesium sulphate and then filtered through a pre-slurried Celite bed, which is washed through with toluene. The filtrate is concentrated to dryness and the solid thus obtained is then recrystallized twice from ethyl acetate/methanol. Yield: 49.5 g (70 mmol), 70%. Purity: about 97% by .sup.1H NMR.

[0301] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00021 Ex. Reactants Product Yield S601 S501 [00944] 74% S602 S504 [00945] 71% S603 S503 [00946] 73% S604 S505 [00947] 81%

Example S610

[0302] ##STR00948##

[0303] Analogous to F. Diness et al., Angew. Chem. Int. Ed., 2012, 51, 8012. A mixture of 35.3 g (50 mmol) of S600, 11.8 g (100 mmol) of benzimidazole and 97.9 g (300 mmol) of caesium carbonate in 500 ml of N,N-dimethylacetamide is heated to 175 C. in a stirred autoclave for 16 h. After cooling, the solvent is substantially drawn off and the residue is taken up in 500 ml of toluene, washed three times with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution, dried over magnesium sulphate and then filtered through a pre-slurried Celite bed. After the solvent has been removed under reduced pressure, the residue is recrystallized from ethyl acetate/methanol. Yield: 33.0 g (41 mmol), 82%. Purity: about 97% by .sup.1H NMR.

[0304] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00022 Ex. Reactants Product Yield S611 [00949] [00950] 74% S612 [00951] [00952] 64% S613 [00953] [00954] 78% S614 [00955] [00956] 75% S615 [00957] [00958] 70% S616 [00959] [00960] 64% S617 [00961] [00962] 68%

Example S620

[0305] ##STR00963##

[0306] To a mixture of 12.6 g (50 mmol) of 4-tert-butyl-2H-pyrimido[2,1-a]isoquinolin-2-one, 12.7 g (50 mmol) of bis(pinacolato)diborane [73183-34-3] and 200 ml of mesitylene are added 1.7 g (2.5 mmol) of bis[(1,2,5,6-)-1,5-cyclooctadiene]di--methoxydiiridium(I) [12148-71-9] and then 1.4 g (5 mmol) of 4,4-di-tert-butyl-[2,2]bipyridinyl [72914-19-3], and then the mixture is stirred at 120 C. for 16 h. After cooling, the solvent is removed under reduced pressure, the residue is taken up in dichloromethane and filtered through a pre-slurried Celite bed, and the filtrate is concentrated to dryness and then chromatographed with dichloromethane:ethyl acetate (9:1) on silica gel. Yield: 8.0 g (21 mmol), 42%; purity: about 95% by .sup.1H NMR.

[0307] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00023 Product Ex. Reactant Boronic ester Yield S621 [00964] [00965] 31% S622 [00966] [00967] 37% S623 [00968] [00969] 17% S624 [00970] [00971] 27% S625 [00972] [00973] 51% S626 [00974] [00975] 13% S627 [00976] [00977] 23% S628 [00978] [00979] 21%

Example S650

[0308] ##STR00980##

[0309] A sodium methoxide solution is prepared from 11.5 g (500 mmol) of sodium and 1000 ml of methanol. To the latter are added, while stirring, 43.6 g (250 mmol) of dimethyl 1,3-acetonedicarboxylate [1830-54-2] and the mixture is stirred for a further 10 min. Then 21.0 g (100 mmol) of 1,7-phenanthroline-5,6-dione [82701-91-5] are added in solid form. After stirring under reflux for 16 h, the methanol is removed under reduced pressure. To the residue are cautiously added 1000 ml of glacial acetic acid (caution: foaming!), and to the brown solution are added 60 ml of water and 180 ml of conc. hydrochloric acid. The reaction mixture is heated under reflux for 16 h, then allowed to cool, poured onto 5 kg of ice and neutralized while cooling by addition of solid sodium hydroxide solution. The precipitated solids are filtered off with suction, washed three times with 300 ml each time of water and dried under reduced pressure. The crude product is stirred in 1000 ml of dichloromethane at 40 C. for 1 h and then filtered while still warm through a Celite bed in order to remove insoluble fractions. After the dichloromethane has been removed under reduced pressure, the residue is dissolved in 100 ml of dioxane at boiling and then 500 ml of methanol are added dropwise starting from 80 C. After cooling and stirring at room temperature for a further 12 h, the solids are filtered off with suction, washed with a little methanol and dried under reduced pressure. Yield: 18.3 g (63 mmol), 63%; purity: about 90% by .sup.1H NMR. The product thus obtained is converted further without purification.

Example S651

[0310] ##STR00981##

[0311] A mixture of 21.0 g (100 mmol) of S650, 50.1 g (1 mol) of hydrazine hydrate, 67.3 g (1.2 mol) of potassium hydroxide and 400 ml of ethylene glycol is heated under reflux for 4 h. Then the temperature is increased gradually and the water formed and excess hydrazine hydrate are distilled off on a water separator. After 16 h under reflux, the reaction mixture is allowed to cool, poured into 2 l of water and extracted three times with 500 ml each time of dichloromethane. The dichloromethane phase is washed five times with 300 ml each time of water and twice with 300 ml each time of saturated sodium chloride solution, and dried over magnesium sulphate.

[0312] After the dichloromethane has been removed under reduced pressure, the oily residue is chromatographed on silica gel with dichloromethane (Rf about 0.5). For further purification, the pale yellow oil thus obtained can be subjected to Kugelrohr distillation or recrystallized from methanol. Yield: 15.5 g (59 mmol), 59%; purity: about 97% by .sup.1H NMR.

Examples S660 and S661

[0313] ##STR00982##

[0314] A mixture of 10.0 g (50 mmol) of 2-bromoacetophenone [2142-69-0], 11.3 g (50 mmol) of 2-bromo-4-tert-butylacetophenone [147438-85-5] and 1.5 g (10 mmol) of trifluoromethanesulphonic acid [1493-13-6] is stirred at 140 C. on a water separator for 18 h. After cooling, the residue is taken up in 300 ml of ethyl acetate, washed three times with 100 ml each time of water and once with 100 ml of saturated sodium chloride solution, and then dried over magnesium sulphate. The crude product is chromatographed (Torrent from Axel Semrau). Yield based on acetophenone groups: S660: 2.6 g (4.3 mmol), 12%; S661: 2.5 g (3.8 mmol) 11%. Purity in each case: about 97% by .sup.1H NMR.

[0315] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00024 Ex. Reactants Products Yield S662 [00983] [00984] 11% S663 as S662 [00985] 10% S664 [00986] [00987] 12% S665 as S664 [00988] 14% S666 [00989] [00990] 16% S667 as S666 [00991] 17%

Example S680

[0316] ##STR00992##

[0317] To a mixture of 29.7 g (100 mmol) of S200, 11.0 g (110 mmol) of trimethylsilylacetylene [1066-54-2], 300 ml of DMF and 20.8 ml (150 mmol) of triethylamine [121-44-8] are added 762 mg (4 mmol) of copper(I) iodide [7681-65-4] and then 1.4 g (2 mmol) of bis(triphenylphosphino)palladium(II) chloride [13965-03-2], and then the mixture is stirred at 80 C. for 6 h. After cooling, the precipitated triethylammonium hydrochloride is filtered off, the filtrate is concentrated to dryness under reduced pressure, the residue is taken up in 300 ml of DCM and filtered through a pre-slurried Celite bed, and the filtrate is washed three times with 100 ml each time of water and once with 100 ml of saturated sodium chloride solution, and dried over magnesium sulphate. The magnesium sulphate is filtered off, the filtrate is concentrated under reduced pressure, the oily residue is taken up in 300 ml of methanol, 27.6 g (200 mmol) of potassium carbonate [584-08-7] and 50 g of glass beads (diameter 3 mm) are added, the mixture is stirred at room temperature for 12 h, the potassium carbonate and glass beads are filtered off using a pre-slurried Celite bed and the filtrate is concentrated completely under reduced pressure. Yield: 22.7 g (89 mmol), 89%; purity: about 95% by .sup.1H NMR. The product thus obtained is converted further without purification.

[0318] In an analogous manner, it is possible to prepare the following compound:

TABLE-US-00025 Ex. Reactant Product Yield S681 [00993] [00994] 90%

B: Synthesis of Ligands and Ligand Precursors LPart 1

Example L1

[0319] ##STR00995##

[0320] Variant A:

[0321] A mixture of 54.1 g (100 mmol) of 1,3,5-tris(2-bromophenyl)benzene, S50, [380626-56-2], 141.9 g (350 mmol) of 2-[1,1,2,2,3,3-hexamethylindan-5-yl]-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)pyridine S21, 106.0 g (1 mol) of sodium carbonate, 5.8 g (5 mmol) of tetrakis(triphenylphosphino)palladium(0), or alternatively triphenyl- or tri-o-tolylphosphine and palladium(II) acetate in a molar ratio of 3:1, 750 ml of toluene, 200 ml of ethanol and 500 ml of water is heated under reflux with very good stirring for 24 h. After 24 h, 300 ml of 5% by weight aqueous acetylcysteine solution are added, the mixture is stirred under reflux for a further 16 h and allowed to cool, the aqueous phase is removed and the organic phase is concentrated to dryness. The brown foam is taken up in 300 ml of ethyl acetate and filtered through a silica gel bed pre-slurried with ethyl acetate (diameter 15 cm, length 20 cm) in order to remove brown components. After concentrating to 200 ml, the solution is added dropwise to 1000 ml of methanol with very good stirring, in the course of which a beige solid precipitates out. The solid is filtered off with suction, washed twice with 200 ml each time of methanol and dried under reduced pressure. The reprecipitation process is repeated again. Yield: 54.7 g (48 mmol), 48%. Purity: about 95% by .sup.1H NMR.

[0322] Remaining secondary components are frequently the disubstitution product and/or the debrominated disubstitution product. A purity of about 90% or even less is sufficient for use in the o-metallation reaction. The ligands can be purified further if required by chromatography on silica gel (n-heptane or cyclohexane or toluene in combination with ethyl acetate, dichloromethane, acetone, etc., optionally with addition of a polar protic component such as methanol or acetic acid). Alternatively, it is possible to recrystallize ligands lacking bulky alkyl groups from ethyl acetate or acetonitrile, optionally with addition of MeOH or EtOH. Ligands having a molar mass of less than about 1000-1200 g/mol can be subjected to Kugelrohr sublimation under high vacuum (p about 10.sup.5 mbar).

[0323] The NMR spectra of the ligandsespecially those of ligands having bridged sub-ligandsare frequently complex, since there are frequently mixtures of syn and anti rotamers in solution.

Example L2

[0324] ##STR00996##

[0325] Variant B:

[0326] Procedure analogous to Example L1, with S21 replaced by S22.

[0327] Purification: After the organic phase from the Suzuki coupling has been concentrated, the brown foam is taken up in 300 ml of a mixture of dichloromethane:ethyl acetate (8:1, v/v) and filtered through a silica gel bed pre-slurried with dichloromethane:ethyl acetate (8:1, v/v) (diameter 15 cm, length 20 cm), in order to remove brown components. After concentration, the remaining foam is recrystallized from 800 ml of ethyl acetate with addition of 400 ml of methanol at boiling and then for a second time from 1000 ml of pure ethyl acetate and then subjected to Kugelrohr sublimation under high vacuum (p about 10.sup.5 mbar, T 280 C.). Ligands having a molar mass greater than about 1000-1200 g/mol are used without Kugelrohr sublimation/distillation. Yield: 50.6 g (66 mmol), 66%. Purity: about 99.7% by .sup.1H NMR.

[0328] Variant C:

[0329] Procedure analogous to Example L1, with replacement of S21 by S22, of the sodium carbonate by 127.4 g (600 mmol) of tripotassium phosphate [7778-53-2] and of the tetrakis(triphenylphosphino)palladium(0) by 1.6 g (4 mmol) of SPhos [657408-07-6] and 674 mg (3 mmol) of palladium(II) acetate [3375-31-3]. Purification: as under Variant B. Yield: 40.6 g (53 mmol), 53%. Purity: about 99.5% by .sup.1H NMR.

[0330] Variant D:

[0331] The aqueous phase is extracted five times with 200 ml of DCM. The combined organic phases are freed of the solvent. The residue is taken up in 1000 ml of DCM:acetonitrile:methanol 1:1:0.1 and filtered through Celite. The filtrate is freed of the solvent under reduced pressure, and the residue is extracted by stirring from 300 ml of hot methanol and then dried under reduced pressure.

[0332] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00026 Bromide Boronic acid/ ester/ tetrafluoro- Ex. borate Product Variant Yield L3 S50 S23 [00997] 63% L4 S50 S24 [00998] 72% L5 S50 S25 [00999] 58% L6 S50 S26 [01000] 60% L7 S50 S27 [01001] 58% L8 S50 S28 [01002] 51% L9 S50 S29 [01003] 52% L10 S50 S30 [01004] 51% L11 S50 S31 [01005] 47% L12 S50 S32 [01006] 50% L13 S50 S33 [01007] 53% L14 S50 S34 [01008] 43% L15 S50 S35 [01009] 40% L16 S50 S36 [01010] 54% L17 S50 S37 [01011] 59% L18 S50 S38 [01012] 45% L19 S50 S39 [01013] 57% L20 S50 S40 [01014] 60% L21 S50 S41 [01015] 62% L22 S50 S42 [01016] 60% L23 S50 S43 [01017] 57% L24 S44 S22 [01018] 43% L25 S44 S34 [01019] 40% L26 S45 S22 [01020] 59% L27 S46 S36 [01021] 55% L28 S47 S22 [01022] 62% L29 S47 S33 [01023] 49% L30 S48 S22 [01024] 38% L31 S49 S28 [01025] 40% L32 S51 S24 [01026] 69% L33 S52 S34 [01027] 53% L34 S53 S21 [01028] 64% L35 syn + anti S7 S22 [01029] 46% L36 syn + anti S7 S34 [01030] 39% L37 S50 S54 [01031] 71% L38 S50 S55 [01032] 62% L63 S50 S57 [01033] 57% L63 S50 S58 [01034] 49% L72 [01035] [01036] 58% L74 [01037] [01038] 28% L76 S50 S62 [01039] 34% L91 S50 S97 [01040] 38% L92 S50 S98 [01041] 41% L93 S50 S99 [01042] 37% L94 S50 S100 [01043] 34% L95 S101 S22 [01044] 50% L96 [01045] [01046] 56% L97 [01047] [01048] 48% L98 [01049] [01050] 66% L99 [01051] [01052] 34% L100 [01053] [01054] 37% L101 [01055] [01056] 46% L102 [01057] [01058] 54% L103 [01059] [01060] 58% L104 [01061] [01062] 50% L105 [01063] [01064] 63% L106 [01065] [01066] 55% L107 [01067] [01068] 30% L108 [01069] [01070] 28% 48% L109 [01071] [01072] 34% L111 [01073] [01074] 56% L112 [01075] [01076] 64% L113 [01077] [01078] 51% L114 [01079] [01080] 68% L116 [01081] [01082] 57% L117 [01083] [01084] 64% L118 [01085] [01086] 62% L119 [01087] [01088] 68% L120 [01089] [01090] 70% L121 [01091] [01092] 72% L122 [01093] [01094] 84% L123 [01095] [01096] 67% L124 [01097] [01098] 51% L125 [01099] [01100] 68% L126 [01101] [01102] 62% L127 [01103] [01104] 71% L128 [01105] [01106] 70% L129 [01107] [01108] 66% L130 [01109] [01110] 75% L131 [01111] [01112] 81% L132 [01113] [01114] 80% L133 [01115] [01116] 58% L134 [01117] [01118] 79% L135 [01119] [01120] 68% L136 [01121] [01122] 58% L137 [01123] [01124] 61% L138 [01125] [01126] 70% L139 [01127] [01128] 69% L140 [01129] [01130] 66% L141 [01131] [01132] 80% L142 [01133] [01134] 77% L143 [01135] [01136] 54% L144 [01137] [01138] 61% L145 [01139] [01140] 64% L146 [01141] [01142] 67% L147 [01143] [01144] 70% L148 [01145] [01146] L149 [01147] [01148] 28%

Example L39

[0333] ##STR01149##

[0334] a) L39-Intermediate1

##STR01150##

[0335] A mixture of 54.1 g (100 mmol) of 1,3,5-tris(2-bromophenyl)benzene, S50, [380626-56-2], 40.5 g (100 mmol) of 2-[1,1,2,2,3,3-hexamethylindan-5-yl]-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)pyridine S21, also referred to hereinafter as boronic ester 1, 31.8 g (300 mmol) of sodium carbonate, 1.2 g (1 mmol) of tetrakis(triphenylphosphino)palladium(0), 300 ml of toluene, 100 ml of ethanol and 200 ml of water is heated under reflux with very good stirring for 24 h. After cooling, the aqueous phase is removed and the organic phase is concentrated to dryness. The brown foam is taken up in 300 ml of ethyl acetate and filtered through a silica gel bed pre-slurried with ethyl acetate (diameter 15 cm, length 20 cm) in order to remove brown components. Subsequently, the foam is chromatographed twice on silica gel (n-heptane:ethyl acetate 5:1). Yield: 25.2 g (34 mmol), 34%. Purity: about 95% by .sup.1H NMR.

[0336] b) L39

[0337] A mixture of 22.3 g (30 mmol) of L39-Intermediate), 22.5 g (80 mmol) of 2-phenyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)pyridine, S22, also referred to hereinafter as boronic ester 2, 63.6 g (600 mmol) of sodium carbonate, 3.5 g (3 mmol) of tetrakis(triphenylphosphino)palladium(0), 600 ml of toluene, 200 ml of ethanol and 400 ml of water is heated under reflux with very good stirring for 24 h. After 24 h, 200 ml of 5% by weight aqueous acetylcysteine solution are added, the mixture is stirred under reflux for a further 16 h and allowed to cool, the aqueous phase is removed and the organic phase is concentrated to dryness. The brown foam is taken up in 300 ml of ethyl acetate and filtered through a silica gel bed pre-slurried with ethyl acetate (diameter 15 cm, length 20 cm) in order to remove brown components. After concentrating to 200 ml, the solution is added dropwise to 1000 ml of methanol with very good stirring, in the course of which a beige solid precipitates out. The solids are filtered off with suction, washed twice with 200 ml each time of methanol and dried under reduced pressure. The reprecipitation process is repeated again. Subsequently, the foam is chromatographed twice on silica gel (n-heptane:ethyl acetate 3:1). Yield: 16.0 g (18 mmol), 60%. Purity: about 99.0% by .sup.1H NMR.

[0338] Remaining secondary components are frequently the disubstitution product and/or the debrominated disubstitution product. The purity is sufficient to be able to use the ligand in the o-metallation reaction. The ligands can be purified further if required by repeated chromatography on silica gel (n-heptane or cyclohexane or toluene in combination with ethyl acetate). Alternatively, it is possible to recrystallize the ligands from ethyl acetate, optionally with addition of MeOH or EtOH. Ligands having a molar mass of less than about 1000-1200 g/mol can be subjected to Kugelrohr sublimation under high vacuum (p about 10.sup.5 mbar).

[0339] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00027 Bromide boronic Ex. acid/ester 1 and 2 Product Yield L40 S50 1 S22 2 S21 [01151] 20% L41 S50 1 S23 2 S22 [01152] 22% L42 S50 1 S24 2 S22 [01153] 25% L43 S50 1 S22 2 S24 [01154] 24% L44 S50 1 S25 2 S22 [01155] 18% L45 S50 1 S26 2 S22 [01156] 21% L46 S50 1 S22 2 S27 [01157] 20% L47 S50 1 S28 2 S30 [01158] 17% L48 S50 1 S34 2 S22 [01159] 20% L49 S50 1 S31 2 S34 [01160] 23% L50 S50 1 S35 2 S34 [01161] 23% L51 S50 1 S36 2 S22 [01162] 20% L52 S50 1 S34 2 S36 [01163] 24% L53 S46 1 S34 2 S36 [01164] 19% L54 S47 1 S22 2 S36 [01165] 20% L55 S50 1 S40 2 S22 [01166] 24% L56 S50 1 S40 2 S36 [01167] 22% L57 S50 1 S41 2 S22 [01168] 26% L58 S50 1 S22 2 S43 [01169] 25% L71 S50 1 S60 2 S22 [01170] 28% L73 S50 [01171] 1 [908350-80-1] 2 S22 [01172] 24% L75 S50 [01173] 1 [562098-24-2] 2 S22 [01174] 19% L77 S50 1 S83 2 S22 [01175] 17% L78 S50 1 S83 2 S34 [01176] 25% L79 S50 1 S84 2 S34 [01177] 27% L80 S50 1 S85 2 S22 [01178] 25% L81 S50 1 S86 2 S22 [01179] 23% L82 S50 1 S87 2 S22 [01180] 26% L83 S50 1 S88 2 S22 [01181] 30% L84 S50 1 S89 2 S36 [01182] 22% L85 S50 1 S90 2 S22 [01183] 21% L86 S50 1 S91 2 S22 [01184] 25% L87 S50 1 S92 2 S22 [01185] 25% L88 S50 1 S93 2 S22 [01186] 27% L89 S50 1 S95 2 S22 [01187] 24% L90 S50 1 S96 2 S22 [01188] 26%

Example L200

[0340] ##STR01189##

[0341] A mixture of 69.1 g (100 mmol) of S501, 42.5 g (110 mmol) of S204, 63.7 g (300 mmol) of tripotassium phosphate, 1.64 g (4 mmol) of SPhos [657408-07-6], 449 mg (2 mmol) of palladium(II) acetate, 700 ml of toluene, 300 ml of dioxane and 500 ml of water is heated under reflux for 8 h. After cooling, the organic phase is removed, washed twice with 300 ml of water and once with 200 ml of saturated sodium chloride solution, dried over magnesium sulphate and then filtered through a pre-slurried Celite bed, which is washed through with toluene. The filtrate is concentrated to dryness and the residue is then recrystallized twice from ethyl acetate/methanol. Yield: 45.5 g (54 mmol), 54%. Purity: about 97% by .sup.1H NMR.

[0342] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00028 Ex. Reactants Product Yield L71 S500 S213 [01190] 76% L201 S501 S200 [01191] 74% L202 S501 S205 [01192] 70% L203 S502 S205 [01193] 71% L204 S502 S206 [01194] 76% L205 S502 S209 [01195] 77% L206 S503 S205 [01196] 81% L207 S503 S208 [01197] 77% L208 S503 S211 [01198] 68% L209 S504 S200 [01199] 75% L210 S504 S213 [01200] 80% L211 S504 S201 [01201] 69% L212 S505 S202 [01202] 75% L213 S505 S206 [01203] 76% L214 S505 S207 [01204] 71% L215 S505 S208 [01205] 70% L216 S505 S209 [01206] 73% L217 S505 S211 [01207] 69% L218 S505 S212 [01208] 80% L219 S505 S210 [01209] 68% L220 S502 S203 [01210] 70% L221 S502 S214 [01211] 67% L222 S502 S215 [01212] 70% L223 S502 S216 [01213] 63% L224 S505 S217 [01214] 70% L225 S505 S220 [01215] 68% L226 S504 S218 [01216] 75% L227 S502 S219 [01217] 48% L228 S502 S221 [01218] 66% L229 S505 S225 [01219] 57% L230 S505 S226 [01220] 69% L231 S502 S222 [01221] 64% L232 S502 S223 [01222] 67% L233 S505 S224 [01223] 61%

Example L250

[0343] ##STR01224##

[0344] To a solution of 40.3 g (50 mmol) of S610 in 300 ml of DCM are added dropwise 18.8 ml (300 mmol) of methyl iodide [74-88-4] and the mixture is heated to 60 C. in a stirred autoclave for 24 h. After cooling, the solvent and excess methyl iodide are drawn off under reduced pressure. The ligand precursor thus obtained is converted without further purification. Yield: 61.5 g (50 mmol), quantitative. Purity: about 95% by .sup.1H NMR.

[0345] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00029 Ex. Reactants Product Yield L251 S611 [01225] quant. L252 S612 [01226] 15502-33-4 [01227] Dioxan, 140 C. quant. L253 S613 [01228] quant. L254 S614 [01229] quant. L255 S615 [01230] quant. L256 S616 [01231] quant. L257 S617 D.sub.3CI 865-50-9 [01232] quant.

Example L260

[0346] ##STR01233##

[0347] A mixture of 16.1 g (20 mmol) of S610, 23.9 g (85 mmol) of diphenyliodonium tetrafluoroborate [313-39-3], 363 mg (2 mmol) of copper(II) acetate [142-71-2] in 200 ml of DMF is heated to 100 C. for 8 h. After cooling, the solvent is removed under reduced pressure, the residue is taken up in a mixture of 100 ml of dichloromethane, 100 ml of acetone and 20 ml of methanol and filtered through a silica gel bed, and the core fraction is extracted and concentrated to dryness. The ligand precursor thus obtained is converted without further purification. Yield: 22.1 g (17 mmol) 85%. Purity: about 90% by .sup.1H NMR.

[0348] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00030 Ex. Reactants Product Yield L261 S615 [01234] 89%

Example L270

[0349] ##STR01235##

[0350] Procedure according to Ex. L2. Use of 12.0 g (20 mmol) of S660 and 19.7 g (70 mmol) of S22, the remaining components are adjusted proportionally. Yield: 10.7 g (13 mmol) 65%. Purity: 98% by .sup.1H NMR.

[0351] In an analogous manner, it is possible to synthesize the following compounds:

TABLE-US-00031 Ex. Reactants Product Yield L271 S661 S103 [01236] 69% L272 S662 S121 [01237] 60% L273 S663 S118 [01238] 65% L274 S664 S627 [01239] 70% L275 S665 S93 [01240] 49% L276 S666 S36 [01241] 64% L277 S667 S60 [01242] 71%

Example L59

[0352] ##STR01243##

[0353] a) L59-Intermediate1=L39-Intermediate1

##STR01244##

[0354] b) L59-Intermediate2

##STR01245##

[0355] A mixture of 74.2 g (100 mmol) of L59-Intermediate1, 28.1 g (100 mmol) of 2-phenyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)pyridine, S22, also referred to hereinafter as boronic ester 2, 31.8 g (300 mmol) of sodium carbonate, 1.2 g (1 mmol) of tetrakis(triphenylphosphino)palladium(0), 300 ml of toluene, 100 ml of ethanol and 200 ml of water is heated under reflux with very good stirring for 24 h. After cooling, the aqueous phase is removed and the organic phase is concentrated to dryness. The brown foam is taken up in 300 ml of ethyl acetate and filtered through a silica gel bed pre-slurried with ethyl acetate (diameter 15 cm, length 20 cm) in order to remove brown components. Subsequently, the foam is chromatographed twice on silica gel (n-heptane:ethyl acetate 5:1). Yield: 29.4 g (36 mmol), 36%. Purity: about 95% by .sup.1H NMR.

[0356] c) L59

[0357] A mixture of 24.5 g (30 mmol) of L59-Intermediate2, 22.5 g (40 mmol) of 2,4-diphenyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)pyridine, S36, also referred to hereinafter as boronic ester 3, 10.6 g (100 mmol) of sodium carbonate, 633 mg (0.6 mmol) of tetrakis(triphenylphosphino)palladium(0), 100 ml of toluene, 70 ml of ethanol and 150 ml of water is heated under reflux with very good stirring for 24 h. After 24 h, 100 ml of 5% by weight aqueous acetylcysteine solution are added, the mixture is stirred under reflux for a further 16 h and allowed to cool, the aqueous phase is removed and the organic phase is concentrated to dryness. The brown foam is taken up in 300 ml of ethyl acetate and filtered through a silica gel bed pre-slurried with ethyl acetate (diameter 15 cm, length 20 cm) in order to remove brown components. After concentrating to 100 ml, the solution is added dropwise to 500 ml of methanol with very good stirring, in the course of which a beige solid precipitates out. The solid is filtered off with suction, washed twice with 100 ml each time of methanol and dried under reduced pressure. The reprecipitation process is repeated again. Subsequently, the foam is chromatographed twice on silica gel (n-heptane:ethyl acetate 3:1). Yield: 15.4 g (16 mmol), 53%. Purity: about 99.0% by .sup.1H NMR.

[0358] Remaining secondary components are frequently the disubstitution product and/or the debrominated disubstitution product. The purity is sufficient to use the ligands in the o-metallation reaction. The ligands can be purified further if required by repeated chromatography on silica gel (n-heptane or cyclohexane or toluene in combination with ethyl acetate). Alternatively, it is possible to recrystallize the ligands from ethyl acetate, optionally with addition of MeOH or EtOH. Ligands having a molar mass of less than about 1000-1200 g/mol can be subjected to Kugelrohr sublimation under high vacuum (p about 10.sup.5 mbar).

[0359] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00032 Bromide Boronic acid/ ester 1, Ex. 2 and 3 Product Yield L60 S50 S22 S24 S36 [01246] 11% L61 S50 S22 S26 S27 [01247] 10% L62 S50 S22 S33 S40 [01248] 13%

Example L65

[0360] ##STR01249##

[0361] Procedure analogous to Example L1, with replacement of S21 by 103.7 g (350 mmol) of 2-(4-methylphenyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazine [1402172-34-2]. Purification: After the organic phase from the Suzuki coupling has been concentrated, the brown foam is taken up in 300 ml of a mixture of dichloromethane:ethyl acetate (8:1, v/v) and filtered through a silica gel bed pre-slurried with dichloromethane:ethyl acetate (8:1, v/v) (diameter 15 cm, length 20 cm), in order to remove brown components. After concentration, the remaining foam is recrystallized three times from 600 ml of ethyl acetate and then subjected to Kugelrohr sublimation under high vacuum (p about 10.sup.5 mbar, T=290 C.). Yield: 38.9 g (48 mmol), 48%. Purity: about 99.5% by .sup.1H NMR.

[0362] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00033 Bromide/boronic Ex. acid or ester Product Yield L66 S50 [01250] [1264510-78-2] [01251] 53% L67 S50 [01252] [1258867-70-7] [01253] 46% L110 S50 S61 [01254] 63%

Example L68

[0363] ##STR01255##

[0364] a) L68 Intermediate1=L39-Intermediate1

[0365] For preparation see L39.

[0366] b) L68:

[0367] A mixture of 22.3 g (30 mmol) of L68-Intermediate1, 22.5 g (80 mmol) of 5-borono-2-pyridinecarboxylic acid [913836-11-0], also referred to hereinafter as boronic ester 2, 63.6 g (600 mmol) of sodium carbonate, 3.5 g (3 mmol) of tetrakis(triphenylphosphino)palladium(0), 600 ml of toluene, 200 ml of ethanol and 400 ml of water is heated under reflux with very good stirring for 24 h. After cooling, the mixture is cautiously neutralized by adding 10 N hydrochloric acid, the aqueous phase is removed and re-extracted with 200 ml of ethyl acetate, and the combined organic phases are filtered through Celite and then concentrated to dryness. The residue is recrystallized three times from DMF with addition of ethanol and then twice from acetonitrile. Yield: 10.7 g (13 mmol), 43%. Purity: about 99.0% by .sup.1H NMR.

[0368] Remaining secondary components are frequently the disubstitution product and/or the debrominated disubstitution product. The purity is sufficient to use the ligands in the o-metallation reaction. The ligands can be purified further if required by repeated chromatography on silica gel (n-heptane or cyclohexane or toluene in combination with ethyl acetate). Alternatively, it is possible to recrystallize the ligands from ethyl acetate, optionally with addition of MeOH or EtOH. Ligands having a molar mass of less than about 1000-1200 g/mol can be subjected to Kugelrohr sublimation under high vacuum (p about 10.sup.5 mbar).

[0369] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00034 Bromide boronic acid/ester Ex. 1 and 2 Product Yield L69 S50 [01256] 1 [913836-11-0] 2 S22 [01257] 26% L70 S50 1 S56 2 S22 [01258] 21%

Example L280

[0370] ##STR01259##

[0371] To a well-stirred suspension, cooled to 0 C., of 2.4 g (100 mmol) of sodium hydride in 200 ml of THF is added dropwise a solution of 15.2 g (100 mmol) of (1R)-(+)-camphor [464-49-3] in 100 ml of THF (caution: evolution of hydrogen). After stirring at 0 C. for a further 15 min and at room temperature for a further 30 min, the reaction mixture is admixed with 21.4 g (30 mmol) of L124 and then stirred under reflux for 5 h. After cooling, quenching is effected by cautious addition of 5% by weight hydrochloric acid to pH=8. The mixture is extended with 300 ml of water and 300 ml of ethyl acetate, the organic phase is removed, the aqueous phase is extracted three times with 200 ml each time of ethyl acetate, and the organic phases are combined and washed twice with 300 ml of water and once with 300 ml of saturated sodium chloride solution and then dried over magnesium sulphate. The yellow oil obtained after removal of the ethyl acetate is dissolved in 200 ml of ethanol, 21.0 ml (150 mmol) of hydrazine hydrate are added dropwise while stirring and then the mixture is heated under reflux for 16 h. After cooling, the solvent is removed under reduced pressure, and the residue is dissolved in 500 ml of ethyl acetate, washed twice with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and then dried over magnesium sulphate. The residue obtained after the solvent has been removed is recrystallized twice from acetonitrile/ethyl acetate. Yield: 14.6 g (13.8 mmol), 46%. Purity: about 97.0% by .sup.1H NMR.

Example L290

[0372] ##STR01260##

[0373] A mixture of 71.2 g (100 mmol) of L124, 22.4 g (400 mmol) of KOH, 400 ml of ethanol and 100 ml of water is heated under reflux for 8 h. The solvent is substantially removed under reduced pressure, 300 ml of water are added and the mixture is acidified with acetic acid to pH 5-6. The mixture is extracted five times with 200 ml of dichloromethane each time and the combined extracts are dried over magnesium sulphate. The crude product obtained after the solvent has been removed is converted without further purification. Yield: 63.6 g (95 mmol), 92%. Purity: about 95.0% by .sup.1H NMR.

Example L2: Preparation by Cyclotrimerization of Alkynes

[0374] ##STR01261##

[0375] To a solution of 25.5 g (100 mmol) of S680 in 200 ml of dioxane are added 1.8 g (10 mmol) of dicarbonylcyclopentadienylcobalt [12078-25-0] and the mixture is heated under reflux for three days. After cooling, the solvent is removed under reduced pressure, and the residue is taken up in dichloromethane and filtered through a pre-slurried silica gel bed. After concentration, the remaining foam is recrystallized from 200 ml of ethyl acetate with addition of 100 ml of methanol at boiling and then for a second time from 400 ml of pure ethyl acetate and then subjected to Kugelrohr sublimation under high vacuum (p about 10.sup.5 mbar, T 280 C.). Yield: 20.7 g (27 mmol), 81%. Purity: about 99.5% by .sup.1H NMR.

[0376] In an analogous manner, it is possible to prepare L111 from S681; yield: 77%.

Example L2: Preparation from 2,2,2-(1,3,5-benzenetriyl)tris [4,4,5,5-tetramethyl-1,3,2-dioxaborolane

[0377] Procedure according to Ex. L2, Variant B. Use of 45.6 g (100 mmol) of 2,2,2-(1,3,5-benzenetriyl)tris[4,4,5,5-tetramethyl-1,3,2-dioxaborolane [365564-05-2] and 96.2 g (310 mmol) of S200; the remaining components are adjusted proportionally. Yield: 52.1 g (68 mmol) 68%. Purity: 98% by .sup.1H NMR.

[0378] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00035 Boronic ester Ex. bromide Product Yield L300 365564-05-2 [01262] S222 [01263] 41% L301 365564-05-2 [01264] S223 [01265] 62% L302 365564-05-2 [01266] S224 [01267] 60%

C: Synthesis of the Metal ComplexesPart 1

Example Ir(L1)

[0379] ##STR01268##

[0380] Variant A:

[0381] A mixture of 11.39 g (10 mmol) of ligand L1, 4.90 g (10 mmol) of trisacetylacetonatoiridium(III) [15635-87-7] and 120 g of hydroquinone [123-31-9] is initially charged in a 500 ml two-neck round-bottomed flask with a glass-sheathed magnetic core. The flask is provided with a water separator (for media of lower density than water) and an air condenser with argon blanketing. The flask is placed in a metal heating bath. The apparatus is purged with argon from the top via the argon blanketing system for 15 min, allowing the argon to flow out of the side neck of the two-neck flask. Through the side neck of the two-neck flask, a glass-sheathed Pt-100 thermocouple is introduced into the flask and the end is positioned just above the magnetic stirrer core. Then the apparatus is thermally insulated with several loose windings of domestic aluminium foil, the insulation being run up to the middle of the riser tube of the water separator. Then the apparatus is heated rapidly with a heated laboratory stirrer system to 250-260 C., measured with the Pt-100 thermal sensor which dips into the molten stirred reaction mixture. Over the next 1.5 h, the reaction mixture is kept at 250-260 C., in the course of which a small amount of condensate is distilled off and collects in the water separator. After cooling, the melt cake is mechanically comminuted and extracted by boiling with 500 ml of methanol. The beige suspension thus obtained is filtered through a double-ended frit, and the beige solid is washed once with 50 ml of methanol and then dried under reduced pressure. Crude yield: quantitative. The solid thus obtained is dissolved in 200 ml of dichloromethane and filtered through about 1 kg of dichloromethane-preslurried silica gel (column diameter about 18 cm) with exclusion of air in the dark, leaving dark-coloured components at the start. The core fraction is cut out and concentrated on a rotary evaporator, with simultaneous continuous dropwise addition of MeOH until crystallization. After removal with suction, washing with a little MeOH and drying under reduced pressure, the orange product is purified further by continuous hot extraction five times with toluene/acetonitrile 3:1 (v/v) and hot extraction twice with ethyl acetate (amount initially charged in each case about 150 ml, extraction thimble: standard Soxhlet thimbles made from cellulose from Whatman) with careful exclusion of air and light. Finally, the product is heat-treated at 330 C. under high vacuum. Yield: 11.15 g (8.4 mmol), 84%. Purity: >99.9% by HPLC.

Example Ir(L2)

[0382] ##STR01269##

[0383] Variant B:

[0384] Procedure analogous to Ir(L1). Crude yield: quantitative. The solid thus obtained is dissolved in 1500 ml of dichloromethane and filtered through about 1 kg of dichloromethane-preslurried silica gel (column diameter about 18 cm) with exclusion of air in the dark, leaving dark-coloured components at the start. The core fraction is cut out and substantially concentrated on a rotary evaporator, with simultaneous continuous dropwise addition of MeOH until crystallization. After removal with suction, washing with a little MeOH and drying under reduced pressure, the yellow product is purified further by continuous hot extraction three times with toluene/acetonitrile (3:1, v/v) and hot extraction five times with toluene (amount initially charged in each case about 150 ml, extraction thimble: standard Soxhlet thimbles made from cellulose from Whatman) with careful exclusion of air and light. Finally, the product is subjected to fractional sublimation twice under high vacuum at p about 10.sup.5 mbar and T about 380 C. Yield: 7.74 g (8.1 mmol), 81%. Purity: >99.9% by HPLC.

[0385] Variant C:

[0386] Procedure analogous to Ir(L2) Variant B, except that 300 ml of diethylene glycol [111-46-6] are used rather than 120 g of hydroquinone and the mixture is stirred at 225 C. for 16 h. After cooling to 70 C., the mixture is diluted with 300 ml of ethanol, and the solids are filtered off with suction (P3), washed three times with 100 ml each time of ethanol and then dried under reduced pressure. Further purification is effected as described in Variant B. Yield: 7.35 g (7.7 mmol), 77%. Purity: >99.9% by HPLC.

[0387] Variant C*:

[0388] Procedure analogous to Ir(L2) Variant B, except that 300 ml of ethylene glycol [107-21-1] are used rather than 120 g of hydroquinone and the mixture is stirred under reflux for 24 h. After cooling to 70 C., the mixture is diluted with 300 ml of ethanol, and the solids are filtered off with suction (P3), washed three times with 100 ml each time of ethanol and then dried under reduced pressure. Further purification is effected as described in Variant B. Yield: 7.54 g (7.9 mmol), 79%. Purity: >99.9% by HPLC.

[0389] Variant D:

[0390] Procedure analogous to Ir(L2) Variant B, except that 3.53 g (10 mmol) of iridium(III) chloriden H.sub.2O (n about 3) are used rather than 4.90 g (10 mmol) of trisacetylacetonatoiridium(III) [15635-87-7] and 300 ml of diethylene glycol [111-46-6] rather than 120 g of hydroquinone, and the mixture is stirred at 225 C. for 16 h. After cooling to 70 C., the mixture is diluted with 300 ml of ethanol, and the solids are filtered off with suction (P3), washed three times with 100 ml each time of ethanol and then dried under reduced pressure. Further purification is effected as described in Variant B. Yield: 5.64 g (5.9 mmol), 59%. Purity: >99.9% by HPLC.

[0391] Variant E: Tris-Carbene Complexes

[0392] A suspension of 20 mmol of the carbene ligand and 60 mmol of Ag.sub.2O in 300 ml of dioxane is stirred at 30 C. for 12 h. Then 10 mmol of [Ir(COD)Cl].sub.2 [12112-67-3] are added and the mixture is heated under reflux for 8 h. The solids are filtered off while the mixture is still hot and they are washed three times with 50 ml each time of hot dioxane, and the filtrates are combined and concentrated to dryness under reduced pressure. The crude product thus obtained is chromatographed twice on basic alumina with ethyl acetate/cyclohexane or toluene. The product is purified further by continuous hot extraction five times with acetonitrile and hot extraction twice with ethyl acetate/methanol (amount initially charged in each case about 200 ml, extraction thimble: standard Soxhlet thimbles made from cellulose from Whatman) with careful exclusion of air and light. Finally, the product is sublimed and/or heat-treated under high vacuum. Purity: >99.8% by HPLC.

[0393] Variant F: Complexes with a Mixed Phenylpyridine and Carbene Coordination Set

[0394] Procedure analogous to Variant A, except that 2.5 g (20 mmol) of 4-dimethylaminopyridine [112258-3] and 2.3 g (10 mmol) of silver(I) oxide [20667-12-3] are added to the reaction mixture.

[0395] The metal complexes are typically obtained as a 1:1 mixture of the and isomers/enantiomers. Images of complexes adduced hereinafter typically show only one isomer. If ligands having three different sub-ligands are used, or chiral ligands are used as a racemate, the metal complexes derived are obtained as a diastereomer mixture. These can be separated by fractional crystallization or by chromatographic means. If chiral ligands are used in enantiomerically pure form, the metal complexes derived are obtained as a diastereomer mixture, the separation of which by fractional crystallization or chromatography leads to pure enantiomers.

[0396] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00036 Variant Ligand Reaction time* Metal Reaction temperature* Ex. synthon* Product Extractant* Yield Rh(L2) L2 Rh(acac).sub.3 14284- 92-5 Rh(L2) [01270] B 56% Ir(L3) L3 Ir(L3) A 76% C 78% Ru(L3) L3 Ru(L3) B 48% RuCl.sub.3 * 3H2O 13815- 94-6 Ir(L4) L4 Ir(L4) A 72% C 69% Ir(L5) L5 Ir(L5) A 64% Ir(L6) L6 Ir(L6) A 71% Ir(L7) L7 Ir(L7) A 70% Ir(L8) L8 Ir(L8) A 63% Ir(L9) L9 Ir(L9) A 69% Ir(L10) L10 Ir(L10) A 77% D 51% Ir(L11) L11 Ir(L11) A 74% Ir(L12) L12 Ir(L12) A 69% Ir(L13) L13 Ir(L13) A 75% Ir(L14) L14 Ir(L14) B 80% o-xylene Ir(L15) L15 Ir(L15) A 78% Ir(L16) L16 Ir(L16) A 74% Ir(L17) L17 Ir(L17) A 77% Ir(L18) L18 Ir(L18) A 54% Ir(L19) L19 Ir(L19) B 67% 12 h o-xylene Ir(L20) L20 Ir(L20) B 51% 10 h 260 C. Ir(L21) L21 Ir(L21) B 59% 16 h o-xylene Ir(L22) L22 Ir(L22) B 62% 16 h Ir(L23) L23 Ir(L23) B 54% 16 h 270 C. Ir(L24) L24 Ir(L24) A 67% Ir(L25) L25 Ir(L25) A 69% Ir(L26) L26 Ir(L26) A 73% Ir(L27) L27 Ir(L27) B 64% Ir(L28) L28 Ir(L28) B 76% Ir(L29) L29 Ir(L29) A 71% Ir(L30) L30 Ir(L30) A 51% Ir(L31) L31 Ir(L31) A 55% Ir(L32) L32 Ir(L32) A 70% C 71% Ir(L33) L33 Ir(L33) A 38% Ir(L34) L34 Ir(L34) B 42% Ir(L35) L35 Ir(L35) B 68% Ir(L36) L36 Ir(L36) B 65% Ir(L37) L37 Ir(L37) B 70% Ir(L38) L38 Ir(L38) B 66% Ir(L39) L39 Ir(L39) A 61% Ir(L40) L40 Ir(L40) A 58% Ir(L41) L41 Ir(L41) B 69% Ir(L42) L42 Ir(L42) B 64% Ir(L43) L43 Ir(L43) B 64% Ir(L44) L44 Ir(L44) B 59% Ir(L45) L45 Ir(L45) B 66% Ir(L46) L46 Ir(L46) B 70% D 56% Ir(L47) L47 Ir(L47) B 59% cyclohexane:toluene (1:1, v/v) Ir(L48) L48 Ir(L48) B 61% Ir(L49) L49 Ir(L49) B 64% Ir(L50) L50 Ir(L50) B 67% Ir(L51) L51 Ir(L51) B 69% Rh(L51) L51 Rh(L51) B 60% Rh(acac).sub.3 14284- 92-5 Ir(L52) L52 Ir(L52) B 60% cyclohexane:toluene (1:1, v/v) Ir(L53) L53 Ir(L53) B 59% cyclohexane:toluene (1:1, v/v) Ir(L54) L54 Ir(L54) B 66% Ir(L55) L55 Ir(L55) B 67% Ir(L56) L56 Ir(L56) B 70% Ir(L57) L57 Ir(L57) B 65% Ir(L58) L58 Ir(L58) B 53% Ir(L59) L59 Ir(L59) B 60% cyclohexane:toluene (1:1, v/v) diaseteromer mixture Ir(L60) L60 Ir(L60) B 62% diastereomer mixture Ir(L61) L61 Ir(L61) B 65% cyclohexane:toluene (1:1, v/v) diastereomer mixture Ir(L62) L62 Ir(L62) B 58% diastereomer mixture Ir(L63) L63 Ir(L63) B 68% Ir(L64) L64 Ir(L64) B 44% Ir(L65) L65 Ir(L65) B 39% Ir(L66) L66 Ir(L66) B 43% Ir(L67) L67 Ir(L67) B 40% Ir(L68) L68 Ir(L68) [01271] C 67% Ir(L69) L69 Ir(L69) C 70% Ir(L70) L70 Ir(L70) C 65% Ir(L71) L71 Ir(L71) B 74% Rh(L71) L71 Rh(L71) B 70% Rh(acac).sub.3 14284- 92-5 Ir(L72) L72 Ir(L72) [01272] B 74% Ir(L72) L72 Ir(L72) C* 68% Ir(L73) L73 Ir(L73) [01273] B 58% Ir(L75) L75 Ir(L75) [01274] D Addition of 30 mmol of 2,6-dimethylpyridine Purification by recrystallization from DMF/acetonitrile 34% Ir(L77) L77 Ir(L77) B 70% Ir(L78) L78 Ir(L78) B 58% Ir(L79) L79 Ir(L79) B 61% Ir(L80) L80 Ir(L80) B 65% Ir(L81) L81 Ir(L81) B 67% Ir(L82) L82 Ir(L82) B 71% Ir(L83) L83 Ir(L83) B 65% Ir(L84) L84 Ir(L84) B 66% Ir(L85) L85 Ir(L85) B 58% Ir(L86) L86 Ir(L86) B 57% Ir(L87) L87 Ir(L87) B 61% Ir(L88) L88 Ir(L88) B 58% Ir(L89) L89 Ir(L89) B 58% Ir(L90) L90 Ir(L90) B 50% Ir(L95) L95 Ir(L95) B 55% Ir(L96) L96 Ir(L96) B 72% Ir(L97) L97 Ir(L97) [01275] B ethyl acetate 30% Ir(L98) L98 Ir(L98) B 66% mesitylene Ir(L99) L99 Ir(L99) B 51% Ir(L100) L100 Ir(L100) B 40% Ir(L101) L101 Ir(L101) B 48% Ir(L102) L102 Ir(L102) B 63% Ir(L103) L103 Ir(L103) B 31% Ir(L104) L104 Ir(L104) A 34% Ir(L105) L105 Ir(L105) B 54% Ir(L106) L106 Ir(L106) B 67% Ir(L107) L107 Ir(L107) [01276] E 39% Ir(L108) L108 Ir(L108) E 33% Ir(L109) L109 Ir(L109) E 27% Ir(L110) L110 Ir(L110) B 56% Ir(L111) L111 Ir(L111) B 85% Rh(L111) L111 Rh(L111) B 71% Rh(acac).sub.3 14284- 92-5 Ru(L111) L111 Ru(L111) B 36% RuCl.sub.3 * 3H2O 13815- 94-6 Ir(L112) L112 Ir(L112) B 81% Ir(L113) L113 Ir(L113) B 61% 260 C./5 h Ir(L114) L114 Ir(L114) 265 C./6 h 58% B Ir(L116) L116 Ir(L116) B 40% 265 C. 2 h mesitylene Ir(L117) L117 Ir(L117) as Ir(L116) 39% Ir(L118) L118 Ir(L118) as Ir(L116) 42% diastereomer mixture Chromatographic separation with DCM on silica gel possible Ir(L119) L119 Ir(L119) as Ir(L116) 58% Ir(L120) L120 Ir(L120) [01277] as Ir(L116) 66% Ir(L121) L121 Ir(L121) as Ir(L116) 53% Ir(L122) L122 Ir(L122) as Ir(L116) 59% Ir(L123) L123 Ir(L123) as Ir(L116) 62% Ir(L125) L125 Ir(L125) B 66% 255 C. 2.5 h Ir(L126) L126 Ir(L126) as Ir(L125) 63% Ir(L127) L127 Ir(L127) B 64% ethyl acetate Ir(L128) L128 Ir(L128) as Ir(L127) 58% Ir(L129) L129 Ir(L129) as Ir(L127) 55% Ir(L130) L130 Ir(L130) B 60% toluene Ir(L131) L131 Ir(L131) B 63% mesitylene Ir(L132) L132 Ir(L132) as Ir(L127) 36% Ir(L133) L133 Ir(L133) as Ir(L131) 44% Ir(L134) L134 Ir(L134) as Ir(L131) 40% Ir(L135) L135 Ir(L135) B 75% dichloromethane Ir(L136) L136 Ir(L136) [01278] B 250 C./2 h ethyl acetate 44% Ir(L137) L137 Ir(L137) as Ir(L136) 51% Ir(L138) L138 Ir(L138) as Ir(L136) 73% Ir(L139) L139 Ir(L139) as Ir(L136) 70% Ir(L140) L140 Ir(L140) as Ir(L97) 68% Ir(L141) L141 Ir(L141) as Ir(L97) 61% Ir(L142) L142 Ir(L142) as Ir(L97) 65% Ir(L143) L143 Ir(L143) as Ir(L97) 37% Ir(L144) L144 Ir(L144) [01279] B o-xylene 63% Ir(L145) L145 Ir(L145) Ir(L144) 55% Ir(L146) L146 Ir(L146) Ir(L144) 66% Ir(L147) L147 Ir(L147) Ir(L144) 68% Ir(L148) L148 Ir(L148) Ir(L144) 48% Ir(L149) L149 Ir(L149) [01280] B 31% Ir(L200) L200 Ir(L200) B 73% Ir(L201) L201 Ir(L201) B 70% ethyl acetate Ir(L202) L202 Ir(L202) as Ir(L201) 67% Ir(L203) L203 Ir(L203) as Ir(L201) 70% Ir(L204) L204 Ir(L204) as Ir(L201) 70% Ir(L205) L205 Ir(L205) as Ir(L201) 73% Ir(L206) L206 Ir(L206) as Ir(L201) 75% Ir(L207) L207 Ir(L207) B 75% n-butyl acetate Ir(L208) L208 Ir(L208) as Ir(L201) 72% Ir(L209) L209 Ir(L209) as Ir(L201) 70% Ir(L210) L210 Ir(L210) B 76% Ir(L211) L211 Ir(L211) as Ir(L201) 75% Ir(L212) L212 Ir(L212) as Ir(L201) 68% Ir(L213) L213 Ir(L213) as Ir(L201) 79% Ir(L214) L214 Ir(L214) as Ir(L201) 67% Ir(L215) L215 Ir(L215) as Ir(L201) 70% Ir(L216) L216 Ir(L216) as Ir(L201) 71% Ir(L217) L217 Ir(L217) as Ir(L201) 66% Ir(L218) L218 Ir(L218) B 69% Ir(L219) L219 Ir(L219) B 55% fluorobenzene Ir(L22) L220 Ir(L220) as Ir(L201) 63% Os(L220) L220 Os(L220) C 39% Chromatography with DCM on alox, neutral Ir(L221) L221 Ir(L221) as Ir(L201) 67% Ir(L222) L222 Ir(L222) B 64% butyl acetate Ir(L223) L223 Ir(L223) B 57% butyl acetate It(L224) L224 It(L224) as Ir(L223) 61% Ir(L225) L225 Ir(L225) as Ir(L201) 33% Ir(L226) L226 Ir(L226) B 14% Ir(L227) L227 Ir(L227) as Ir(L201) 21% Ir(L228) L228 Ir(L228) as Ir(L201) 26% Ir(L229) L229 Ir(L229) B 67% mesitylene Ir(L230) L230 Ir(L230) as Ir(L229) 63% Ir(L231) L231 Ir(L231) B 50% Ir(L232) L232 Ir(L232) B 61% Ir(L233) L233 Ir(L233) [01281] B butyl acetate 63% Ir(L250) L250 Ir(L250) [01282] F 2 hot ethyl acetate extraction 5 hot toluene extraction 31% Ir(L251) L251 Ir(L251) as Ir(L250) 40% Ir(L252) L252 Ir(L252) as Ir(L250) 38% Ir(L253) L253 Ir(L253) as Ir(L250) 27% Ir(L254) L254 Ir(L254) as Ir(L250) 33% Ir(L255) L255 Ir(L255) as Ir(L250) 30% Ir(L256) L256 Ir(L256) as Ir(L250) 30% Ir(L257) L257 Ir(L257) as Ir(L250) 40% Ir(L260) L260 Ir(L260) as Ir(L250) 40% Ir(L261) L261 Ir(L261) as Ir(L250) 42% Ir(L270) L270 Ir(L270) [01283] B 65% Ir(L271) L271 Ir(L271) as Ir(L270) 70% Ir(L272) L272 Ir(L272) as Ir(L270) 61% Ir(L273) L273 Ir(L273) as Ir(L270) 64% Ir(L274) L274 Ir(L274) as Ir(L270) 64% Ir(L275) L275 Ir(L275) B 48% 2.5 h 265 C. dichloromethane Ir(L276) L276 Ir(L276) as Ir(L270) 70% Ir(L277) L277 Ir(L277) as Ir(L270) 69% Ir(L300) L300 Ir(L300) B 27% Ir(L301) L301 Ir(L301) B 48% It(L302) L302 It(L302) B 66% toluene *Stated if different from general method

[0397] Metal Complexes of Ligand L74:

##STR01284##

[0398] To a solution of 769 mg (1 mmol) of L74 in 10 ml of DMSO is added dropwise, at 75 C., a solution, heated to 75 C., of 1 mmol of the appropriate metal salt in 20 ml of EtOH or EtOH/water (1:1 v/v) and the mixture is stirred for a further 5 h. If appropriate, with addition of 6 mmol of the appropriate salt (KPF.sub.6, (NH.sub.4)PF.sub.6, KBF.sub.4, etc.) in 10 ml of EtOH or EtOH/water (1:1, v/v), an anion exchange is conducted. After cooling, the microcrystalline precipitate is filtered off with suction, washed with cold MeOH and dried under reduced pressure. The purification can be effected by recrystallization from acetonitrile/methanol.

[0399] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00037 Ex. Ligand Metal salt Product Yield M1 L74 [Fe(L74)](ClO.sub.4).sub.2 68% Fe(ClO.sub.4).sub.2 M2 L74 [Fe(L74)](ClO.sub.4).sub.3 76% Fe(ClO.sub.4).sub.3 M3 L74 [Ru(L74)](ClO.sub.4).sub.3 70% Ru(ClO.sub.4).sub.3 M4 L74 [Os(L74)](ClO.sub.4).sub.2 39% Os(ClO.sub.4).sub.2 M5 L74 [Co(L74)](ClO.sub.4).sub.3 63% Co(ClO.sub.4).sub.3 M6 L74 [Rh(L74)](PF.sub.6).sub.3 58% RhCl.sub.3 H.sub.2O KPF.sub.6 M7 L74 [Ir(L74)](PF.sub.6).sub.3 69% (NH.sub.4).sub.3[IrCl.sub.6] H.sub.2O KPF.sub.6 M8 ZnCl.sub.2 [Zn(L74)](BF.sub.4).sub.3 73% KBF.sub.4

[0400] Metal Complexes of Ligand L76:

##STR01285##

[0401] To a solution of 736 mg (1 mmol) of L76 and 643 mg (6 mmol) of 2,6-dimethylpyridine in 10 ml of DMSO is added dropwise, at 75 C., a solution, heated to 75 C., of 1 mmol of the appropriate metal salt in 20 ml of EtOH or EtOH/water (1:1 v/v) and the mixture is stirred for a further 10 h. If appropriate, with addition of 6 mmol of the appropriate salt (KPF.sub.6, (NH.sub.4)PF.sub.6, KBF.sub.4, etc.) in 10 ml of EtOH or EtOH/water (1:1, v/v), an anion exchange is conducted. After cooling, the microcrystalline precipitate is filtered off with suction, washed with cold MeOH and dried under reduced pressure. The purification can be effected by recrystallization from acetonitrile/methanol.

[0402] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00038 Ex. Ligand Metal salt Product Yield M100 L76 Fe(L76) 68% FeCl.sub.3 hydrate M101 L76 NH.sub.4[Ru(L76)] 47% [Ru(NH.sub.3).sub.6]Cl.sub.2 no 2,6- dimethylpyridine M102 L76 Ru(L76) 56% RuCl.sub.3 hydrate M103 L76 Os(L76) 61% OsCl.sub.3 hydrate M104 L76 Rh(L76) 47% RhCl.sub.3 hydrate M105 L76 Ir(L76) 72% IrCl.sub.3 hydrate M106 L76 [Pt(L76)](PF.sub.6) 64% (NH.sub.4).sub.2[PtCl.sub.6] added as solid NH.sub.4PF.sub.6

[0403] Metal Complexes of Ligand L91:

##STR01286##

[0404] To a solution of 736 mg (1 mmol) of L91 and 643 mg (6 mmol) of 2,6-dimethylpyridine in 10 ml of DMSO is added dropwise, at 75 C., a solution, heated to 75 C., of 1 mmol of the appropriate metal salt in 20 ml of EtOH or EtOH/water (1:1 v/v) and the mixture is stirred for a further 10 h. If appropriate, with addition of 6 mmol of the appropriate salt (KPF.sub.6, (NH.sub.4)PF.sub.6, KBF.sub.4, etc.) in 10 ml of EtOH or EtOH/water (1:1, v/v), an anion exchange is conducted. After cooling, the microcrystalline precipitate is filtered off with suction, washed with cold MeOH and dried under reduced pressure. The purification can be effected by recrystallization from acetonitrile/methanol.

[0405] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00039 Ex. Ligand Metal salt Product Yield M200 L91 Al(L91) 86% AlCl.sub.3 M201 L91 Ga(L91) 78% GaCl.sub.3 M202 L91 In(L91) 75% InCl.sub.3 M203 L91 La(L91) 44% LaCl.sub.3 M204 L91 Ce(L91) 48% CeCl.sub.3 M205 L91 Fe(L91) 91% FeCl.sub.3 M206 L91 Ru(L91) 88% RuCl.sub.3

[0406] Metal Complexes of Ligand L92:

##STR01287##

[0407] To a solution of 778 mg (1 mmol) of L92 and 643 mg (6 mmol) of 2,6-dimethylpyridine in 10 ml of DMSO is added dropwise, at 75 C., a solution, heated to 75 C., of 1 mmol of the appropriate metal salt in 20 ml of EtOH or EtOH/water (1:1 v/v) and the mixture is stirred for a further 10 h. If appropriate, with addition of 6 mmol of the appropriate salt (KPF.sub.6, (NH.sub.4)PF.sub.6, KBF.sub.4, etc.) in 10 ml of EtOH or EtOH/water (1:1, v/v), an anion exchange is conducted. After cooling, the microcrystalline precipitate is filtered off with suction, washed with cold MeOH and dried under reduced pressure. Purification can be effected by recrystallization from acetonitrile/methanol or by hot extraction and subsequent fractional sublimation. The diastereomer mixtures which form in the case of the chiral ligand L280 can be separated by chromatography on silanized silica gel.

[0408] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00040 Ex. Ligand Metal salt Product Yield M300 L92 Ga(L92) 68% GaCl.sub.3 M301 L92 In(L92) 70% InCl.sub.3 M302 L92 Ir(L92) 76% IrCl.sub.3 hydrate M303 L93 La(L93) 55% LaCl.sub.3 M304 L93 Fe(L93) 86% FeCl.sub.3 M305 L93 Ir(L93) 84% IrCl.sub.3 hydrate M306 L94 Ru(L94) 78% RuCl.sub.3 M307 L94 Ir(L94) 81% IrCl.sub.3 hydrate M308 L280 Al(L280) 58% AlCl.sub.3 diastereomer mixture M309 L280 Fe(L280) 86% FeCl.sub.3 diastereomer mixture M310 L280 Ru(L280) 74% RuCl.sub.3 diastereomer mixture M311 L280 Ir(L280) 79% IrCl.sub.3 hydrate diastereomer mixture

[0409] Metal Complexes of Ligand L290:

##STR01288##

[0410] Procedure analogous to Example M200.

[0411] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00041 Ex. Ligand Metal salt Product Yield M400 L290 Al(L290) 66% AlCl.sub.3 M401 L290 Ga(L290) 70% GaCl.sub.3 M402 L290 La(L290) 48% LaCl.sub.3 M403 L290 Ce(L290) 53% CeCl.sub.3 M404 L290 Fe(L290) 89% FeCl.sub.3 M405 L290 Ru(L290) 87% RuCl.sub.3 M406 L290 Ir(L290) 77% IrCl.sub.3 hydrate

D: Functionalization of the Metal ComplexesPart 1

1) Halogenation of the Iridium Complexes

[0412] To a solution or suspension of 10 mmol of a complex bearing ACH groups (with A=1, 2, 3) in the para position to the iridium in 500 ml to 2000 ml of dichloromethane according to the solubility of the metal complexes is added, in the dark and with exclusion of air, at 30 to +30 C., A x 10.5 mmol of N-halosuccinimide (halogen: CI, Br, I), and the mixture is stirred for 20 h. Complexes of sparing solubility in DCM may also be converted in other solvents (TCE, THF, DMF, chlorobenzene, etc.) and at elevated temperature. Subsequently, the solvent is substantially removed under reduced pressure. The residue is extracted by boiling with 100 ml of methanol, and the solids are filtered off with suction, washed three times with 30 ml of methanol and then dried under reduced pressure. This gives the iridium complexes brominated in the para position to the iridium. Complexes having a HOMO (CV) of about 5.1 to 5.0 eV and of smaller magnitude have a tendency to oxidation (Ir(III)>Ir(IV)), the oxidizing agent being bromine released from NBS. This oxidation reaction is apparent by a distinct green hue in the otherwise yellow to red solutions/suspensions of the emitters. In such cases, a further equivalent of NBS is added. For workup, 300-500 ml of methanol and 2 ml of hydrazine hydrate as reducing agent are added, which causes the green solutions/suspensions to turn yellow (reduction of Ir(IV)>Ir(III)). Then the solvent is substantially drawn off under reduced pressure, 300 ml of methanol are added, and the solids are filtered off with suction, washed three times with 100 ml each time of methanol and dried under reduced pressure.

[0413] Substoichiometric brominations, for example mono- and dibrominations of complexes having 3 CH groups in the para position to iridium, usually proceed less selectively than the stoichiometric brominations. The crude products of these brominations can be separated by chromatography (CombiFlash Torrent from A. Semrau).

[0414] Synthesis of Ir(L2-3Br):

##STR01289##

[0415] To a suspension, stirred at 0 C., of 9.6 g (10 mmol) of Ir(L2) in 2000 ml of DCM are added 5.6 g (31.5 mmol) of N-bromosuccinimide all at once and then the mixture is stirred for a further 20 h. After removing about 1900 ml of the DCM under reduced pressure, 100 ml of methanol are added to the yellow suspension, and the solids are filtered off with suction, washed three times with about 50 ml of methanol and then dried under reduced pressure. Yield: 11.3 g (9.5 mmol), 95%; purity: >99.0% by NMR.

[0416] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00042 Ex. Reactant > brominated complex Yield Tribromination Ir(L14-3Br) [01290] Ir(L14) > Ir(L14-3Br) 95% Ir(L16-3Br) [01291] Ir(L16) > Ir(L16-3Br) 90% Ir(L20-3Br) [01292] Ir(L20) > Ir(L20-3Br) 97% Ir(L22-3Br) [01293] Ir(L22) > Ir(L22-3Br) 96% Ir(L24-3Br) [01294] Ir(L24) > Ir(L24-3Br) 93% Ir(L27-3Br) [01295] Ir(L27) > Ir(L27-3Br) 90% Ir(L35-3Br) [01296] Ir(L35) > Ir(L35-3Br) 95% Ir(L37-3Br) [01297] Ir(L37) > Ir(L37-3Br) 92% Ir(L48-3Br) [01298] Ir(L48) > Ir(L48-3Br) 90% Ir(L51-3Br) [01299] Ir(L51) > Ir(L51-3Br) 90% Ir(L55-3Br) [01300] Ir(L55) > Ir(L55-3Br) 95% Ir(L72-3Br) [01301] Ir(L72) > Ir(L72-3Br) 86% Ir(L73-3Br) [01302] Ir(L73) > Ir(L73-3Br) 91% Ir(L96-3Br) [01303] Ir(L96) > Ir(L96-3Br) 89% Ir(L100-3Br) [01304] Ir(L100) > Ir(L100-3Br) 87% Ir(L101-3Br) [01305] Ir(L101) > Ir(L101-3Br) 46% Ir(L107-3Br) [01306] Ir(L107) > Ir(L107-3Br) Chromatography on silica gel 67% Ir(L111-3Br) [01307] Ir(L111) > Ir(L111-3Br) 96% Ir(L116-3Br) [01308] Ir(L116) > Ir(L116-3Br) 95% Ir(L120-3Br) [01309] Ir(L120) > Ir(L120-3Br) 90% Ir123-3Br [01310] Ir123 > Ir123-3Br Use of 4.15 mmol of NBS Addition of 2 ml of hydrazine hydrate to the MeOH 92% Ir(L203-3Br) [01311] Ir(L203) > Ir(L203-3Br) 95% Ir(L204-3Br) [01312] Ir(L204) > Ir(L204-3Br) 96% Ir(L205-3Br) [01313] Ir(L205) > Ir(L205-3Br) 94% Ir(L212-3Br) [01314] Ir(L212) > Ir(L212-3Br) 96% Ir(L213-3Br) [01315] Ir(L213) > Ir(L213-3Br) 95% Ir(L216-3Br) [01316] Ir(L216) > Ir(L216-3Br) 95% Ir(L218-3Br) [01317] Ir(L218) > Ir(L218-3Br) 95% Ir150-3Br [01318] Ir150 > Ir150-3Br 96% Dibromination Ir(L2-2Br) [01319] Ir(L2) > Ir(L2-2Br) 33% Ir(L39-2Br) [01320] Ir(L39) > Ir(L39-2Br) 63% Ir(L44-2Br) [01321] Ir(L44) > Ir(L44-2Br) 62% Ir(L49-2Br) [01322] Ir(L49) > Ir(L49-2Br) 67% Ir(L71-2Br) [01323] Ir(L71) > Ir(L71-2Br) 96% Ir(L220-2Br) [01324] Ir(L220) > Ir(L220-2Br) DMSO solvent 95% Monobromination Ir(L2-Br) [01325] Ir(L2) > Ir(L2-Br) DMSO solvent 24% Ir(L40-Br) [01326] Ir(L40) > Ir(L40-Br) 64% Ir(L206-Br) [01327] Ir(L206) > Ir(L206-Br) Use of 2.1 mmol of NBS Addition of 2 ml of hydrazine hydrate to the MeOH 93% Ir(L207-Br) [01328] Ir(L207) > Ir(L207-Br) Use of 2.1 mmol of NBS Addition of 2 ml of hydrazine hydrate to the MeOH 94% Ir(L208-Br) [01329] Ir(L208) > Ir(L208-Br) Use of 2.1 mmol of NBS Addition of 2 ml of hydrazine hydrate to the MeOH 89%

2) Suzuki Coupling with the Brominated Iridium Complexes

[0417] Variant A, Biphasic Reaction Mixture:

[0418] To a suspension of 10 mmol of a brominated complex, 12-20 mmol of boronic acid or boronic ester per Br function and 40-80 mmol of tripotassium phosphate in a mixture of 300 ml of toluene, 100 ml of dioxane and 300 ml of water are added 0.6 mmol of tri-o-tolylphosphine and then 0.1 mmol of palladium(II) acetate, and the mixture is heated under reflux for 16 h. After cooling, 500 ml of water and 200 ml of toluene are added, the aqueous phase is removed, and the organic phase is washed three times with 200 ml of water and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulphate. The mixture is filtered through a Celite bed and washed through with toluene, the toluene is removed almost completely under reduced pressure, 300 ml of methanol are added, and the precipitated crude product is filtered off with suction, washed three times with 50 ml each time of methanol and dried under reduced pressure. The crude product is columned on silica gel. The metal complex is finally heat-treated or sublimed. The heat treatment is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 200-300 C. The sublimation is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 300-400 C., the sublimation preferably being conducted in the form of a fractional sublimation.

[0419] Variant B, Monophasic Reaction Mixture:

[0420] To a suspension of 10 mmol of a brominated complex, 12-20 mmol of boronic acid or boronic ester per Br function and 60-100 mmol of the base (potassium fluoride, tripotassium phosphate (anhydrous or monohydrate or trihydrate), potassium carbonate, caesium carbonate etc.) and 100 g of glass beads (diameter 3 mm) in 100 ml-500 ml of an aprotic solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.) are added 0.6 mmol of tri-o-tolylphosphine and then 0.1 mmol of palladium(II) acetate, and the mixture is heated under reflux for 1-24 h. Alternatively, it is possible to use other phosphines such as triphenylphosphine, tri-tert-butylphosphine, Sphos, Xphos, RuPhos, XanthPhos, etc., the preferred phosphine:palladium ratio in the case of these phosphines being 3:1 to 1.2:1. The solvent is removed under reduced pressure, the product is taken up in a suitable solvent (toluene, dichloromethane, ethyl acetate, etc.) and purification is effected as described in Variant A.

[0421] Synthesis of Ir100:

##STR01330##

[0422] Variant A:

[0423] Use of 11.9 g (10.0 mmol) of Ir(L2-3Br) and 9.0 g (60.0 mmol) of 2,5-dimethylphenylboronic acid [85199-06-0], 17.7 g (60 mmol) of tripotassium phosphate (anhydrous), 183 mg (0.6 mmol) of tri-o-tolylphosphine [6163-58-2], 23 mg (0.1 mmol) of palladium(II) acetate, 300 ml of toluene, 100 ml of dioxane and 300 ml of water, reflux, 16 h. Chromatographic separation twice on silica gel with toluene/ethyl acetate (9:1, v/v), followed by hot extraction five times with ethyl acetate/dichloromethane (1:1, v/v). Yield: 6.8 g (5.7 mmol), 57%; purity: about 99.9% by HPLC.

[0424] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00043 Bromide/boronic acid/variant Ex. Product Yield Ir101 [01331] 61% Ir102 [01332] 53% Ir103 [01333] 41% Ir104 [01334] 66% Ir105 [01335] 55% Ir106 [01336] 46% Ir107 [01337] 62% Ir108 [01338] 47% Ir109 [01339] 57% Ir110 [01340] 55% Ir111 [01341] 46% Ir112 [01342] 53% Ir113 [01343] 55% Ir114 [01344] 50% Ir115 [01345] 49% Ir116 [01346] 52% Ir117 [01347] 43% Ir118 [01348] 61% Ir119 [01349] 46% Ir120 [01350] 59% Ir121 [01351] 67% Ir122 [01352] 51% Ir123 [01353] 71% Ir124 [01354] 68% Ir126 [01355] 50% Ir127 [01356] 55% Ir128 [01357] 63% Ir129 [01358] 59% Ir131 [01359] 51% Ir132 [01360] 54% Ir133 [01361] 60% Ir134 [01362] 57% Ir135 [01363] 62% Ir136 [01364] 59% Ir137 [01365] 61% Ir138 [01366] 58% Ir139 [01367] 53% Ir140 [01368] 68% Ir141 [01369] 55% Ir142 [01370] 57% Ir143 [01371] 48% Ir144 [01372] 55% Ir145 [01373] 61% Ir146 [01374] 65% Ir151 [01375] 60% Ir152 [01376] 42% Ir153 [01377] 66% Ir154 [01378] 55%

3) Buchwald Coupling with the Ir Complexes

[0425] To a mixture of 10 mmol of the brominated complex, 12-20 mmol of the diarylamine or carbazole per bromine function, a 1.1 molar amount of sodium tert-butoxide per amine used or 80 mmol of tripotassium phosphate (anhydrous) in the case of carbazoles, 100 g of glass beads (diameter 3 mm) and 300-500 ml of toluene or o-xylene in the case of carbazoles are added 0.4 mmol of tri-tert-butylphosphine and then 0.3 mmol of palladium(II) acetate, and the mixture is heated under reflux with good stirring for 16-30 h. After cooling, 500 ml of water are added, the aqueous phase is removed, and the organic phase is washed twice with 200 ml of water and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulphate. The mixture is filtered through a Celite bed and washed through with toluene or o-xylene, the solvent is removed almost completely under reduced pressure, 300 ml of ethanol are added, and the precipitated crude product is filtered off with suction, washed three times with 50 ml each time of EtOH and dried under reduced pressure. The crude product is purified by chromatography on silica gel or by hot extraction. The metal complex is finally heat-treated or sublimed. The heat treatment is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 200-300 C. The sublimation is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 300-400 C., the sublimation preferably being conducted in the form of a fractional sublimation.

[0426] Synthesis of Ir200:

##STR01379##

[0427] Use of 14.2 g (10 mmol) of Ir(L16-3Br) and 9.7 g (40 mmol) of 3-phenylcarbazole [103012-26-6]. Chromatography with toluene on silica gel three times, heat treatment. Yield: 6.5 g (3.4 mmol), 34%; purity: about 99.8% by HPLC.

[0428] In an analogous manner, it is possible to Prepare the following compounds:

TABLE-US-00044 Reactant/amine or carbazole Ex. Product Yield Ir201 [01380] 39% Ir202 [01381] 67% Ir203 [01382] 27% Ir204 [01383] 23% Ir205 [01384] 28%

4) Cyanation of the Iridium Complexes

[0429] A mixture of 10 mmol of the brominated complex, 13 mmol of copper(I) cyanide per bromine function and 300 ml of NMP is stirred at 180 C. for 20 h. After cooling, the solvent is removed under reduced pressure, the residue is taken up in 500 ml of dichloromethane, the copper salts are filtered off using Celite, the dichloromethane is concentrated almost to dryness under reduced pressure, 100 ml of ethanol are added, and the precipitated solids are filtered off with suction, washed twice with 50 ml each time of ethanol and dried under reduced pressure. The crude product is purified by chromatography and/or hot extraction. The heat treatment is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 200-300 C. The sublimation is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 300-400 C., the sublimation preferably being conducted in the form of a fractional sublimation.

[0430] Synthesis of Ir300:

##STR01385##

[0431] Use of 12.4 g (10 mmol) of Ir(L37-3Br) and 3.5 g (39 mmol) of copper(I) cyanide. Chromatography on silica gel with dichloromethane twice, sublimation. Yield: 5.6 g (4.9 mmol), 49%; purity: about 99.9% by HPLC.

[0432] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00045 Reactant Ex. Cyanation product Ir301 [01386] 44% Ir302 [01387] 44% Ir303 [01388] 51% Ir304 [01389] 60% Ir305 [01390] 58% Ir306 [01391] 62% Ir307 [01392] 64% Ir308 [01393] 60% Ir309 [01394] 67% Ir310 [01395] 67% Ir311 [01396] 72% Ir312 [01397] 68% Ir313 [01398] 64%

5) Borylation of the Iridium Complexes

[0433] A mixture of 10 mmol of the brominated complex, 12 mmol of bis(pinacolato)diborane [73183-34-3] per bromine function, 30 mmol of anhydrous potassium acetate per bromine function, 0.2 mmol of tricyclohexylphosphine, 0.1 mmol of palladium(II) acetate and 300 ml of solvent (dioxane, DMSO, NMP, toluene, etc.) is stirred at 80-160 C. for 4-16 h. After the solvent has been removed under reduced pressure, the residue is taken up in 300 ml of dichloromethane, THF or ethyl acetate and filtered through a Celite bed, the filtrate is concentrated under reduced pressure until commencement of crystallization and about 100 ml of methanol are finally added dropwise in order to complete the crystallization. The compounds can be recrystallized from dichloromethane, ethyl acetate or THF with addition of methanol.

[0434] Synthesis of Ir400:

##STR01399##

[0435] Use of 11.9 g (10 mmol) of Ir(L2-3Br) and 9.1 g (36 mmol) of bis(pinacolato)diborane [73183-34-3], dioxane/toluene 1:1 v/v, 120 C., 16 h, taking up and Celite filtration in THF. Recrystallization from THF:methanol. Yield: 7.3 g (5.5 mmol), 55%; purity: about 99.8% by HPLC.

[0436] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00046 Product Ex. Reactant Yield Ir401 [01400] 39% Ir402 [01401] 48% Ir403 [01402] 55% Ir404 [01403] 63% Ir405 [01404] 48% Ir406 [01405] 68% Ir407 [01406] 60% Ir408 [01407] 76%

6) Suzuki Coupling with the Borylated Iridium Complexes

[0437] Variant A, Biphasic Reaction Mixture:

[0438] To a suspension of 10 mmol of a borylated complex, 12-20 mmol of aryl bromide per (RO).sub.2B function and 80 mmol of tripotassium phosphate in a mixture of 300 ml of toluene, 100 ml of dioxane and 300 ml of water are added 0.6 mmol of tri-o-tolylphosphine and then 0.1 mmol of palladium(II) acetate, and the mixture is heated under reflux for 16 h. After cooling, 500 ml of water and 200 ml of toluene are added, the aqueous phase is removed, and the organic phase is washed three times with 200 ml of water and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulphate. The mixture is filtered through a Celite bed and washed through with toluene, the toluene is removed almost completely under reduced pressure, 300 ml of methanol are added, and the precipitated crude product is filtered off with suction, washed three times with 50 ml each time of methanol and dried under reduced pressure. The crude product is columned twice on silica gel and/or purified by hot extraction. The metal complex is finally heat-treated or sublimed. The heat treatment is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 200-300 C. The sublimation is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 300-400 C., the sublimation preferably being conducted in the form of a fractional sublimation.

[0439] Variant B, Monophasic Reaction Mixture:

[0440] To a suspension of 10 mmol of a borylated complex, 12-20 mmol of aryl bromide per (RO).sub.2B function and 60-100 mmol of the base (potassium fluoride, tripotassium phosphate (anhydrous or monohydrate or trihydrate), potassium carbonate, caesium carbonate etc.) and 100 g of glass beads (diameter 3 mm) in 100 ml-500 ml of an aprotic solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.) are added 0.6 mmol of tri-o-tolylphosphine and then 0.1 mmol of palladium(II) acetate, and the mixture is heated under reflux for 1-24 h. Alternatively, it is possible to use other phosphines such as triphenylphosphine, tri-tert-butylphosphine, Sphos, Xphos, RuPhos, XanthPhos, etc., the preferred phosphine:palladium ratio in the case of these phosphines being 3:1 to 1.2:1. The solvent is removed under reduced pressure, the product is taken up in a suitable solvent (toluene, dichloromethane, ethyl acetate, etc.) and purification is effected as described in Variant A.

[0441] Synthesis of Ir100:

[0442] Variant A:

[0443] Use of 13.3 g (10.0 mmol) of Ir400 and 7.4 g (40.0 mmol) of 1-bromo-2,5-dimethylbenzene [553-94-6], 17.7 g (60 mmol) of tripotassium phosphate (anhydrous), 183 mg (0.6 mmol) of tri-o-tolylphosphine [6163-58-2], 23 mg (0.1 mmol) of palladium(II) acetate, 300 ml of toluene, 100 ml of dioxane and 300 ml of water, 100 C., 16 h. Chromatographic separation twice on silica gel with toluene/ethyl acetate (9:1, v/v). Yield: 6.7 g (5.3 mmol), 53%; purity: about 99.9% by HPLC.

[0444] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00047 Reactants/catalyst/variant/base/solvent Ex. Product Yield Ir125 [01408] 39% Ir130 [01409] 35% Ir147 [01410] 58% Ir148 [01411] 63% Ir149 [01412] 72% Ir150 [01413] 33% Ir155 [01414] 58% Ir156 [01415] 55% Ir157 [01416] 21% Ir158 [01417] 27% Ir159 [01418] 25% Ir160 [01419] 23%

7) Alkylation of Iridium Complexes

[0445] To a suspension of 10 mmol of the complex in 1500 ml of THF are added 50 ml of a freshly prepared LDA solution, 1 molar in THF, and the mixture is stirred at 25 C. for 24 h. Then 200 mmol of the alkylating agent are added all at once with good stirring, liquid alkylating agents being added without dilution and solid alkylating agents as a solution in THF. The mixture is stirred at room temperature for a further 60 min, the THF is removed under reduced pressure and the residue is chromatographed on silica gel. Further purification can be effected by hot extractionas described above. The metal complex is finally heat-treated or sublimed. The heat treatment is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 200-300 C. The sublimation is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 300-400 C., the sublimation preferably being conducted in the form of a fractional sublimation.

[0446] Synthesis of Ir700:

##STR01420##

[0447] Use of 9.8 g (10.0 mmol) of Ir(L14) and 21.7 ml (200 mmol) of 1-bromo-2-methylpropane [78-77-3]. Chromatographic separation twice on silica gel with toluene, followed by hot extraction five times with acetonitrile. Yield: 2.7 g (2.3 mmol), 23%; purity: about 99.7% by HPLC.

[0448] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00048 Reactant/alkylating agent Ex. Product Yield Ir701 [01421] 29% Ir702 [01422] 27% Ir703 [01423] 34% Ir704 [01424] 35% Ir705 [01425] 26%

8) Arylation of Iridium Complexes

[0449] Synthesis of Ir(L98):

##STR01426##

[0450] To a mixture of 10.7 g (10 mmol) of Ir(L97), 14.2 g (60 mmol) of o-dibromobenzene [583-53-9] and 39.1 g (120 mmol) of caesium carbonate in 400 ml of dimethylacetamide (DMAC) are added 578.62 mg (1 mmol) of Xanthphos [161265-03-8] and then 1156 mg (1 mmol) of tetrakis(triphenylphosphino)palladium(0) [14221-01-3], and the mixture is stirred under reflux for 60 h. After cooling, 300 ml of DMAC are removed under reduced pressure, the mixture is diluted with 1000 ml of methanol and stirred for 1 h, and the yellow solids are filtered off with suction, washed with 100 ml of methanol and dried under reduced pressure. The yellow solids are extracted by stirring in a hot mixture of 200 ml of water and 100 ml of methanol, filtered off with suction, washed with methanol and dried under reduced pressure. Further purification is effected as described in C: Synthesis of the metal complexes.

[0451] Yield: 6.9 g (5.3 mmol), 53%; purity: about 99.7% by HPLC.

[0452] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00049 Ex. Reactant = Ir(L97)/dibromoaromatic/product Yield Ir710 [01427] 59% Ir711 [01428] 53% Ir712 [01429] 46%

9) Carbonyl-Containing Ir Complexes, Synthesis of Ir720

[0453] ##STR01430##

[0454] To a suspension of 10.3 g (10 mmol) of Ir304 in 500 ml of THF are added dropwise, at room temperature, 60 ml of a 1 molar phenylmagnesium bromide solution in THF. Subsequently, the reaction mixture is stirred under reflux for another 2 h, then allowed to cool and quenched by dropwise addition of 20 ml of methanol and 20 ml of water. After the solvent has been removed under reduced pressure, the residue is taken up in 300 ml of N,N-dimethylacetamide, 20 ml of aqueous 5 N HCl are added and the mixture is boiled under reflux for 12 h. After the solvent has been removed under reduced pressure, the residue is taken up in 500 ml of toluene, washed three times with 200 ml each time of water, once with 200 ml of saturated sodium carbonate solution and once with 200 ml of saturated sodium chloride solution, and then dried over magnesium sulphate. After the solvent has been removed, further purification is effected by chromatographic separation twice on silica gel with DCM, followed by hot extraction five times with toluene. Yield: 4.8 g (3.8 mmol), 38%; purity: about 99.8% by HPLC.

[0455] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00050 Ex. Reactant/Grignard compound/product Yield Ir721 [01431] 43% Ir722 [01432] 63%

10) Lactam-Containing Ir Complexes

[0456] Synthesis of Ir730:

##STR01433##

[0457] To a solution of 10.7 g (10 mmol) of Ir(L97) in 300 ml of THF are added 1.2 g (50 mmol) of sodium hydride in portions. After stirring at room temperature for 10 minutes, 3.8 ml (40 mmol) of methacryloyl chloride [920-46-7] in 50 ml of THF are added dropwise while cooling with ice. The mixture is allowed to warm up to room temperature and stirred for a further 12 h. After the solvent has been removed under reduced pressure, the residue is taken up in 100 ml of methanol and stirred for a further 30 min, and the precipitated solid is filtered off with suction, washed three times with 50 ml of methanol and dried at 30 C. under reduced pressure. The solids thus obtained are dissolved in 500 ml of DCM, the solution is cooled to 0 C. in an ice/salt bath and then 3.1 ml (40 mmol) of trifluoromethanesulphonic acid [76-05-1] are added dropwise. After stirring at room temperature for 16 h, 50 ml of triethylamine are added dropwise, then the mixture is washed three times with 200 ml each time of water and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulphate, the latter is filtered off using a Celite bed and the filtrate is concentrated to dryness under reduced pressure. The crude product thus obtained is chromatographed with DCM on silica gel and then purified by hot extraction five times with o-xylene. Yield: 5.6 g (4.4 mmol), 44%; purity: about 99.8% by HPLC.

11) Carbonyl-Containing Ir Complexes

[0458] Synthesis of Ir740

##STR01434##

[0459] To a solution of 15.3 g (10 mmol) of Ir144 in 1000 ml of mesitylene are added dropwise, at 60 C. with good stirring, 5.3 ml (60 mmol) of trifluoromethanesulphonic acid [1493-13-6] and then the mixture is stirred for 12 h. After cooling, 300 ml of ice-water are added, the mixture is neutralized with saturated sodium hydrogencarbonate solution, and the organic phase is removed and washed twice with 300 ml each time of water and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulphate. The desiccant is filtered off, the filtrate is concentrated to dryness and the residue is chromatographed twice on silica gel (DCM/ethyl acetate, 9:1 v/v). Subsequent purification by hot extraction five times with ethyl acetate. Yield: 3.9 g (2.7 mmol), 27%; purity: about 99.8% by HPLC.

[0460] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00051 Reactant Ex. Product Yield Ir741 [01435] 34%

12) Alkylation of Ir Complexes with Benzyl Alcohol Function

[0461] Synthesis of the Diastereomer Mixture Ir750:

##STR01436##

[0462] To a suspension of 10.5 g (10 mmol) Ir(L125) in 300 ml of DMF are added, with good stirring, 960 mg (40 mmol) of sodium hydride in portions (caution: evolution of hydrogen). After heating and stirring at 60 C. for 30 min, a mixture of 9.9 g (50 mmol) of (2S)-1-iodo-2-methylbutane [29394-58-9] in 50 ml of DMF is added dropwise and then the mixture is stirred at 80 C. for 16 h. After cooling, all volatile fractions are removed under reduced pressure, and the residue is taken up in 500 ml of DCM, washed three times with 200 ml of water and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulphate. The desiccant is filtered off using a pre-slurried Celite bed, 300 ml of methanol are added to the filtrate and then about 90% of the solvent is distilled off on a rotary evaporator (water bath at 70 C.), the product being obtained as an orange-yellow solid. The solid is filtered off with suction and washed three times with 50 ml each time of methanol and then dried under reduced pressure. Yield: 9.2 g (7.3 mmol) 73% diastereomer mixture.

[0463] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00052 Ex. Reactant/product Yield Ir751 [01437] 69%

[0464] Separation of the Diastereomers of Ir750:

[0465] The diastereomer mixture Ir750 is divided with toluene on silica gel (about 1200 g, column geometry about 1050 cm) into the two enantiomerically pure diastereomers Ir750-1 (Rf about 0.6, 3.7 g) and Ir750-2 (Rf about 0.4, 4.0 g).

[0466] It is possible in an analogous manner to divide the diastereomer mixture of Ir751 into the two enantiomerically pure diastereomers Ir751-1 and Ir751-2.

13) Hydrogenolysis of Ir Complexes with Benzyl Ether Function

[0467] Synthesis of the Enantiomers Ir760-1 and Ir760-2

##STR01438##

[0468] To a solution of 3.7 g (2.9 mmol) of Ir750-1 in 50 ml of toluene and 50 ml of methanol are added 2 ml (10 mmol) of polymethylhydrosiloxane [9004-73-3] and 87 mg (0.5 mmol) of palladium(II)chloride [7647-10-1] and the mixture is stirred in an autoclave at 60 C. for 30 h. After cooling, the solvent is removed under reduced pressure and the residue is chromatographed twice with dichloromethane on silica gel. Further purification is effected by hot extraction with acetonitrile/ethyl acetate (2:1, v/v).

[0469] Yield of Ir760-1: 2.1 g (2.1 mmol), 72%; purity: about 99.8% by HPLC.

[0470] It is possible in an analogous manner to convert Ir750-2.

[0471] In an analogous manner, it is possible the following compounds:

TABLE-US-00053 Ex. Reactant/product Yield Ir761- 1 Ir761- 2 [01439] 67% 64%

[0472] In general, the pure and enantiomers of a complex, compared to the racemate, have much better solubility in organic solvents (dichloromethane, ethyl acetate, acetone, THF, toluene, anisole, 3-phenoxytoluene, DMSO, DMF, etc.) and sublime at much lower temperatures (typically 30-60 C. lower), for example:

[0473] racemate of Ir761, prepared by co-crystallization of equal amounts of Ir761-1 and Ir761-2: solubility in toluene at RT<1 mg/ml, Tsubl.: 390 C./p about 10.sup.5 mbar.

[0474] Ir761-1 or Ir761-2: solubility in toluene at RT about 5 mg/ml, Tsubl.: 350 C./p about 10.sup.5 mbar.

14) Separation of the and Enantiomers of the Metal Complexes by Means of Chromatography on Chiral Columns

[0475] The and enantiomers of the complexes can be separated by means of analytical and/or preparative chromatography on chiral columns by standard laboratory methods, for example separation of Ir110 on ChiralPak AZ-H (from Chiral Technologies INC.) with n-hexane/ethanol (90:10), retention times 18.5 min. and 26.0 min.

15) Deuteration of Ir Complexes

Example: Ir(L14-D9)

[0476] ##STR01440##

[0477] A mixture of 1.0 g (1 mmol) of Ir(L14), 68 mg (1 mmol) of sodium ethoxide, 30 ml of ethanol-D1 and 50 ml of DMSO-D6 is heated in an autoclave to 90 C. for 80 h. After cooling, the solvent is removed under reduced pressure and the residue is chromatographed with DCM on silica gel. Yield: 0.88 g (0.87 mmol), 87%, deuteration level >90%.

[0478] In an analogous manner, it is possible the following compounds:

TABLE-US-00054 Ex. Reactant/product Yield Ir(L52-D3) [01441] 90% Ir(L71-D3) [01442] 87% Ir(L79-D6) [01443] 85% Ir(L204-D3) [01444] 88% Ir(L210-D3) [01445] 89% Ir700-D6 [01446] 83% Ir701-D6 [01447] 85% Ir705-D3 [01448] 83%

16) Cryptates with Two Different Bridging Units

Example Ir800

[0479] ##STR01449##

[0480] To a suspension of 202 mg (1.2 mmol) of 1,3,5-benzenetrimethanol [4464-18-0] in 50 ml of anhydrous DMSO are added 120 mg (5 mmol) of sodium hydride and the mixture is stirred at 60 C. for 1 h. Then 1058 mg (1 mmol) of Ir(L149) are added and the reaction mixture is stirred at 120 C. for 16 h. After cooling, the DMSO is removed under reduced pressure, the residue is taken up in 200 ml of dichloromethane, and the solution is washed three times with 100 ml each time of water and once with 200 ml of saturated sodium chloride solution and then dried over magnesium sulphate. The desiccant is filtered off, the filtrate is concentrated to dryness and the residue is chromatographed with dichloromethane/ethyl acetate (9:1 v/v) on silica gel. Yield: 179 mg (0.16 mmol), 16%; purity: about 99.8% by HPLC.

[0481] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00055 Ex. Reactant/product Yield Ir801 [01450] 37% Ir802 [01451] 34%

17) Polymers Containing the Metal Complexes

[0482] General Polymerization Method for the Bromides or Boronic Acid Derivatives as Polymerizable Group, Suzuki Polymerization

[0483] Variant ABiphasic Reaction Mixture:

[0484] The monomers (bromides and boronic acids or boronic esters, purity by HPLC>99.8%) are dissolved or suspended in the composition specified in the table in a total concentration of about 100 mmol/1 in a mixture of 2 parts by volume of toluene:6 parts by volume of dioxane:1 part by volume of water. Then 2 molar equivalents of tripotassium phosphate are added per Br functionality used, the mixture is stirred for a further 5 min, then 0.03 to 0.003 molar equivalent of tri-ortho-tolylphosphine and then 0.005 to 0.0005 molar equivalent of palladium(II) acetate (ratio of phosphine to Pd preferably 6:1) per Br functionality used are added and the mixture is heated under reflux with very good stirring for 2-3 h. If the viscosity of the mixture rises too significantly, dilution is possible with a mixture of 2 parts by volume of toluene:3 parts by volume of dioxane. After a total reaction time of 4-6 h, for end-capping, 0.05 molar equivalent per boronic acid functionality used of a monobromoaromatic and then, 30 min thereafter, 0.05 molar equivalent per Br functionality used of a monoboronic acid or a monoboronic ester are added and the mixture is boiled for a further 1 h. After cooling, the mixture is diluted with 300 ml of toluene, the aqueous phase is removed, and the organic phase is washed twice with 300 ml each time of water, dried over magnesium sulphate, filtered through a Celite bed in order to remove palladium and then concentrated to dryness. The crude polymer is dissolved in THF (concentration about 10-30 g/l) and the solution is allowed to run gradually into twice the volume of methanol with very good stirring. The polymer is filtered off with suction and washed three times with methanol. The reprecipitation operation is repeated five times, then the polymer is dried under reduced pressure to constant weight at 30-50 C.

[0485] Variant BMonophasic Reaction Mixture:

[0486] The monomers (bromides and boronic acids or boronic esters, purity by HPLC>99.8%) are dissolved or suspended in the composition specified in the table in a total concentration of about 100 mmol/1 in a solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.). Then 3 molar equivalents of base (potassium fluoride, tripotassium phosphate (anhydrous, monohydrate or trihydrate), potassium carbonate, caesium carbonate, etc., each in anhydrous form) per Br functionality and the equivalent weight of glass beads (diameter 3 mm) are added, the mixture is stirred for a further 5 min, then 0.03 to 0.003 molar equivalent of tri-ortho-tolylphosphine and then 0.005 to 0.0005 molar equivalent of palladium(II) acetate (ratio of phosphine to Pd preferably 6:1) per Br functionality are added and the mixture is heated under reflux with very good stirring for 2-3 h. Alternatively, it is possible to use other phosphines such as tri-tert-butylphosphine, Sphos, Xphos, RuPhos, XanthPhos, etc., the preferred phosphine:palladium ratio in the case of these phosphines being 2:1 to 1.3:1. After a total reaction time of 4-12 h, for end-capping, 0.05 molar equivalent of a monobromoaromatic and then, 30 min thereafter, 0.05 molar equivalent of a monoboronic acid or a monoboronic ester are added and the mixture is boiled for a further 1 h. The solvent is substantially removed under reduced pressure, the residue is taken up in toluene and the polymer is purified as described in Variant A.

[0487] Monomers M/End-Cappers E:

TABLE-US-00056 [01452] M1 [01453] M2 [01454] M3 [01455] M4 [01456] E1 [01457] E2

[0488] Polymers:

[0489] Composition of the polymers, mmol:

TABLE-US-00057 Polymer M1 M2 M3 M4 Ir complex P1 30 45 Ir(L14-3Br)/10 P2 5 25 40 Ir(L39-2Br)/10 P3 10 40 25 20 Ir404/5

[0490] Molecular weights and yield of the polymers of the invention:

TABLE-US-00058 Polymer Mn [gmol.sup.1] Polydispersity Yield P1 240 000 4.6 71% P2 250 000 2.3 57% P3 200 000 2.2 60%

D: Synthesis of the SynthonsPart 2

Example S1000: 5-Bromo-2-(4-chlorophenyl)pyridine

[0491] ##STR01458##

[0492] Into a 4 l four-neck flask with reflux condenser, argon blanketing, precision glass stirrer and internal thermometer are weighed 129.9 g of 4-chlorophenylboronic acid (810 mmol) [1679-18-1], 250.0 g of 5-bromo-2-iodopyridine (250 mmol) [223463-13-6] and 232.7 g of potassium carbonate (1.68 mol), the flask is inertized with argon, and 1500 ml of acetonitrile and 1000 ml of absolute ethanol are added. 100 g of glass beads (diameter 3 mm) are also added thereto and the suspension is homogenized for 5 minutes. Then 5.8 g of bis(triphenylphosphine)palladium(II) chloride (8.3 mmol) [13965-03-2] are added. The reaction mixture is heated to reflux while stirring vigorously overnight. After cooling, the solvent is removed by rotary evaporation and the residue is worked up by extraction with toluene and water in a separating funnel. The organic phase is washed 2 with 500 ml of water and 1 with 300 ml of saturated sodium chloride solution and dried over anhydrous sodium sulphate, and then the solvent is removed under reduced pressure. The precipitated solid is filtered off with suction and washed with ethanol. The yellow solid obtained is recrystallized from 800 ml of acetonitrile at reflux. A beige solid is obtained. Yield: 152.2 g (567.0 mmol), 70%; purity: about 95% by .sup.1H NMR.

Example S1001: 2-(4-Chlorophenyl)-5-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)pyridine

[0493] ##STR01459##

[0494] Into a 4 l four-neck flask with reflux condenser, precision glass stirrer, heating bath and argon connection are weighed 162.0 g (600 mmol) of S1000, 158.0 g (622 mmol) of bis(pinacolato)diborane [73183-34-3], 180.1 g (1.83 mol) of potassium acetate [127-08-2] and 8.9 g (12.1 mmol) of trans-dichlorobis(tricyclohexylphosphine)palladium(II) [29934-17-6], and 2200 ml of 1,4-dioxane are added. 100 g of glass beads (diameter 3 mm) are also added and the reaction mixture is inertized with argon and stirred under reflux for 24 hours. After cooling, the solvent is removed under reduced pressure, and the residue obtained is worked up by extraction in a separating funnel with 1000 ml of ethyl acetate and 1500 ml of water. The organic phase is washed 1 with 500 ml of water and 1 with 300 ml of saturated sodium chloride solution, dried over anhydrous sodium sulphate and filtered through a silica gel-packed frit. The silica gel bed is washed through 2 with 500 ml of ethyl acetate and the filtrate obtained is concentrated under reduced pressure. The brown solid obtained is recrystallized from 1000 ml of n-heptane at reflux. A beige solid is obtained. Yield: 150.9 g (478 mmol), 80%; purity: 97% by .sup.1H NMR.

Example S1002: Synthesis of Symmetric Triazine Units

2-Chloro-4,6-bis(3,5-di-tert-butylphenyl)[1,3,5]triazine

[0495] ##STR01460##

[0496] A baked-out flask is initially charged with 5.8 g (239 mmol) of magnesium turnings and a solution of 73.0 g (271 mmol) of bromo-3,5-di-tert-butylbenzene [22385-77-9] in 400 ml of dry THF is slowly added dropwise, such that the reaction solution boils constantly under reflux. On completion of addition, the solution is boiled under reflux for a further two hours, then allowed to cool. A further flask is additionally charged with 20.0 g (108.5 mmol) of cyanuric chloride in 400 ml of dry THF and cooled to 0 C. The Grignard reagent is added dropwise in such a way that an internal temperature of 20 C. is not exceeded. On completion of addition, the reaction mixture is allowed to warm up to room temperature overnight. The reaction is quenched by addition of 500 ml of 1 mol/l HCl solution while cooling with ice. The phases are separated and the aqueous phase is extracted 3 times with ethyl acetate. The organic phases are combined and washed with saturated NaCl solution, then dried over sodium sulphate, and the filtrate is concentrated under reduced pressure. The light brown oil obtained is admixed with methanol and heated to reflux. After cooling, the precipitated colourless solid is filtered off with suction, washed with heptane and dried under reduced pressure. Yield: 23.6 g (48 mmol), 47%; purity: about 97% by .sup.1H NMR.

[0497] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00059 Bromine Ex. reactant Product Yield S1003 [01461] [01462] 60% S1004 [01463] [01464] 57%

Example S1005 Synthesis of Asymmetric Triazine Units

2-tert-Butyl-4-(4-tert-butylphenyl)-6-chloro[1,3,5]triazine

[0498] A baked-out flask is initially charged with 3.4 g (140 mmol) of magnesium turnings and a solution of 30.0 g (141 mmol) of 1-bromo-4-tert-butylbenzene [3972-65-4] in 50 ml of dry THF is slowly added dropwise, such that the reaction solution boils constantly under reflux. On completion of addition, the solution is boiled under reflux for a further two hours, then allowed to cool. A further flask is additionally charged with 30.1 g (146 mmol) of 2-tert-butyl-4,6-dichloro[1,3,5]triazine [705-23-7] in 75 ml of dry THF and cooled to 0 C. The Grignard reagent is added dropwise in such a way that an internal temperature of 20 C. is not exceeded. On completion of addition, the reaction mixture is allowed to warm up to room temperature overnight. The reaction is quenched by addition of 200 ml of 1 mol/l HCl solution while cooling with ice. The phases are separated and the aqueous phase is extracted three times with toluene. The organic phases are combined and washed with saturated NaCl solution, then dried over sodium sulphate, and the filtrate is concentrated under reduced pressure. The red-brown oil obtained is used without further purification. Yield: 34 g (112 mmol), 79%; purity: about 90% by .sup.1H NMR.

[0499] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00060 Ex. Triazine Bromide Product Yield S1006 [01465] [01466] [01467] 52% S1007 [01468] [01469] [01470] 61%

Example S1008: 5-Bromo-2-(1,1,2,2,3,3-hexamethylindan-5-yl)pyridine

[0500] ##STR01471##

[0501] Into a 2 l four-neck flask are weighed 76.5 g (242 mmol) of S1001, 65.6 g (245 mmol) of 2-chloro-4,6-diphenyl-[1,3,5]-triazine [3842-55-5], 2.8 g (2.4 mmol) of tetrakis(triphenylphosphine)palladium(0) and 64.3 g (606 mmol) of sodium carbonate, the mixture is inertized, and 1200 ml of degassed toluene and 200 ml of degassed water are added. The reaction mixture is stirred under reflux for 24 hours. After the reaction has ended, the precipitated solid is filtered off and washed 3 with 50 ml of water, 3 with 50 ml of ethanol and 2 with 20 ml of toluene. The grey solid obtained is used without further purification. Yield: 75.5 g (179 mmol), 74%; purity: 98% by .sup.1H NMR.

[0502] In an analogous manner, it is additionally possible to construct the following ligands:

TABLE-US-00061 Ex. Chloride Product Yield S1009 [01472] [01473] 60% S1010 S1002 [01474] 58% S1011 S1005 [01475] 73% S1012 [01476] [01477] 41% S1013 [01478] [01479] 50% S1014 [01480] [01481] 56% S1015 [01482] [01483] 66% S1016 [01484] [01485] 61% S1017 [01486] [01487] 77% S1018 [01488] [01489] 58% S1019 [01490] [01491] 52% S1020 [01492] [01493] 78% S1021 [01494] [01495] 69% S1022 [01496] [01497] 45% S1023 [01498] [01499] 49% S1024 [01500] [01501] 71% S1025 S1003 [01502] 77% S1026 S1004 [01503] 75% S1027 [01504] [01505] 68% S1028 S1006 [01506] 59% S1029 S1007 [01507] 74% S1030 [01508] [01509] 60% S1031 [01510] [01511] 61% S1032 [01512] [01513] 31% S1034 [01514] [01515] 41% S1035 [01516] [01517] 35% S1036 [01518] [01519] 41% S1036 [01520] [01521] 72% S1037 [01522] [01523] 81% S1038 [01524] [01525] 79% S1039 [01526] [01527] 70% S1040 [01528] [01529] 80% S1041 [01530] [01531] 85% S1042 [01532] [01533] 60%

Example S1100: 2,4-Diphenyl-6-{6-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]pyridin-3-yl}[1,3,5]triazine

[0503] ##STR01534##

[0504] Into a 2 l four-neck flask with reflux condenser, precision glass stirrer, heating bath and argon connection are weighed 99.5 g (236.4 mmol) of S1000, 61.6 g (243 mmol) of bis(pinacolato)diborane [73183-34-3], 69.6 g (709 mmol) of potassium acetate [127-08-2], 1.9 g (4.7 mmol) of 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl [657408-07-6] and 800 mg (3.6 mmol) of palladium(II) acetate [3375-31-3], the mixture is inertized and 1000 ml of degassed 1,4-dioxane are added. 100 g of glass beads (diameter 3 mm) are also added, then the reaction mixture is stirred under reflux for 24 hours. After cooling, the solvent is removed under reduced pressure, and the residue obtained is extracted by stirring with a hot mixture of 1000 ml of ethanol and 500 ml of water. The grey solid obtained is filtered off with suction and washed 3 with 100 ml of ethanol, and dried in a vacuum drying cabinet at 70 C. and 30 mbar. Further purification is effected by continuous hot extraction three times (extractant, amount initially charged in each case about 300 ml, extraction thimble: standard Soxhlet thimbles made from cellulose from Whatman) with 1,4-dioxane. A pale yellow solid is obtained. Yield: 90.8 g (177 mmol), 75%; purity: 99% by .sup.1H NMR.

[0505] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00062 Chloride/ Ex. synthon Extractant Product Yield S1101 S1009 cyclohexane [01535] 77% S1102 S1010 cyclohexane [01536] 80% S1103 S1011 acetonitrile [01537] 73% S1104 S1012 ethyl acetate [01538] 75% S1105 S1013 ethyl acetate [01539] 67% S1106 S1014 ethyl acetate [01540] 65% S1107 S1015 cyclohexane [01541] 66% S1108 S1016 cyclohexane [01542] 61% S1109 S1017 o-xylene [01543] 77% S1110 S1018 o-xylene [01544] 76% S1111 S1019 toluene [01545] 78% S1112 S1020 mesitylene [01546] 86% S1113 S1021 toluene [01547] 80% S1114 S1022 toluene [01548] 70% S1115 S1023 ethyl acetate [01549] 59% S1116 S1024 toluene [01550] 65% S1117 S1025 cyclohexane [01551] 72% S1118 S1026 cyclohexane [01552] 70% S1119 S1027 cyclohexane [01553] 78% S1120 S1028 toluene [01554] 80% S1121 S1029 toluene [01555] 74% S1122 S1030 dioxane [01556] 77% S1123 S1031 dioxane [01557] 70% S1124 S1032 acetonitrile [01558] 72% S1125 S1034 ethyl acetate [01559] 65% S1126 S1035 ethanol [01560] 68% S1127 S1036 acetonitrile [01561] 70% S1128 S1036 cyclohexane [01562] 75% S1129 S1037 toluene [01563] 80% S1130 S1038 cyclohexane [01564] 79% S1131 S1039 ethyl acetate [01565] 72% S1132 S1040 ethyl acetate [01566] 74% S1133 S1041 p-xylene [01567] 82% S1134 [01568] [1374216-04-2] ethyl acetate [01569] 78% S1135 [01570] [30314-45-5] chroma- tography [01571] 80% S1136 S1042 toluene [01572] 70% S1137 [01573] [1401421-23-5] dioxane [01574] 74%

E: Synthesis of the Ligands Part 2

Example L1000: 2-[6-[4-[2-[3,5-bis[2-[4-[5-(4,6-diphenyl-1,3,5-triazin-2-yl)-2-pyridyl]phenyl]phenyl]phenyl]phenyl]phenyl]-3-pyridyl]-4,6-diphenyl-1,3,5-triazine

[0506] ##STR01575##

[0507] Into a 2 l four-neck flask with reflux condenser, precision glass stirrer, heating bath and argon connection are weighed 40.0 g (76.1 mmol) of S1100, 12.1 g (22.3 mmol) of 1,3,5-tris(2-bromophenyl)benzene [380626-56-2], 17.2 g (162 mmol) of sodium carbonate, 526 mg (2.0 mmol) of triphenylphosphine [603-35-0] and 150 mg (0.67 mmol) of palladium(II) acetate [3375-31-3], and 400 ml of toluene, 200 ml of ethanol and 200 ml of water are added. The reaction mixture is inertized with argon and stirred under reflux for 48 hours. After cooling, the precipitated grey solid is filtered off with suction and washed 5 with 100 ml of ethanol and then dried in a vacuum drying cabinet at 70 C. Further purification is effected by continuous hot extraction three times (extractant, amount initially charged in each case about 300 ml, extraction thimble: standard Soxhlet thimbles made from cellulose from Whatman) with o-xylene. Derivatives of better solubility can be purified by means of chromatographic methods. A pale yellow solid is obtained. Yield: 23.7 g (177 mmol), 69%; purity: 97% by .sup.1H NMR.

[0508] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00063 Product/ synthon/ Ex. extractant/purification Yield L1001 [01576] 55% S1101 chromatography L1002 [01577] 60% S1102 L1003 [01578] 66% S1103 chromatography L1004 [01579] 70% S1104 toluene L1005 [01580] 62% S1105 toluene L1006 [01581] 60% S1106 toluene L1007 [01582] 71% S1107 ethyl acetate L1008 [01583] 75% S1108 toluene L1009 [01584] 82% S1109 o-xylene L1010 [01585] 80% S1110 toluene L1011 [01586] 81% S1111 toluene L1012 [01587] 88% S1112 p-xylene L1013 [01588] 85% S1113 mesitylene L1014 [01589] 73% S1114 o-xylene L1015 [01590] 55% S1115 ethyl acetate L1016 [01591] 59% S1116 toluene L1016 [01592] 71% S1117 dioxane L1018 [01593] 78% S1118 dioxane L1019 [01594] 78% S1119 toluene L1020 [01595] 80% S1120 toluene L1021 [01596] 74% S1121 o-xylene L1022 [01597] 77% S1122 o-xylene L1023 [01598] 70% S1123 dioxane L1024 [01599] 72% S1124 ethyl acetate L1025 [01600] 65% S1125 toluene L1026 [01601] 68% S1126 n-butanol L1027 [01602] 70% S1127 acetonitrile L1028 [01603] 75% S1128 chromatography L1029 [01604] 80% S1129 o-xylene L1030 [01605] 79% S1130 chromatography L1031 [01606] 72% S1131 ethyl acetate L1032 [01607] 74% S1132 toluene L1033 [01608] 82% S1133 o-xylene L1034 [01609] 76% S1134 toluene L1036 [01610] 70% S1136 toluene L1037 [01611] 68% S1137 toluene

[0509] In an analogous manner, it is possible to prepare the following ligands:

TABLE-US-00064 Boronic Ex. ester Bromide Product Yield L1035 [01612] [908350-80-1] [01613] [1690315-37-7] [01614] 70%

F: Synthesis of the Metal ComplexesPart 2

Example Ir(L1000)

[0510] ##STR01615##

[0511] Variant A:

[0512] A mixture of 14.6 g (10 mmol) of ligand L1000, 4.9 g (10 mmol) of trisacetylacetonatoiridium(III) [15635-87-7] and 180 g of hydroquinone [123-31-9] is initially charged in a 1000 ml two-neck round-bottomed flask with a glass-sheathed magnetic core. The flask is provided with a water separator (for media of lower density than water) and an air condenser with argon blanketing. The flask is placed in a metal heating bath. The apparatus is purged with argon from the top via the argon blanketing system for 15 min, allowing the argon to flow out of the side neck of the two-neck flask. Through the side neck of the two-neck flask, a glass-sheathed Pt-100 thermocouple is introduced into the flask and the end is positioned just above the magnetic stirrer core. Then the apparatus is thermally insulated with several loose windings of domestic aluminium foil, the insulation being run up to the middle of the riser tube of the water separator. Then the apparatus is heated rapidly with a heated laboratory stirrer system to 250 C. (reaction temperature), measured with the Pt-100 thermal sensor which dips into the molten stirred reaction mixture. Over the next 2 h (reaction time), the reaction mixture is kept at 250 C., in the course of which a small amount of condensate is distilled off and collects in the water separator. After cooling to 100 C., 500 ml of methanol are cautiously added to the melt cake, and boiled until a red suspension forms. The red suspension thus obtained is filtered through a double-ended frit (P3), and the red solid is washed three times with 100 ml of methanol and then dried under reduced pressure. Crude yield: quantitative. The red product is purified further by continuous hot extraction five times with ethyl acetate (extractant, amount initially charged in each case about 150 ml, extraction thimble: standard Soxhlet thimbles made from cellulose from Whatman) with careful exclusion of air and light. Finally, the product is heat-treated (p about 10.sup.6 mbar, T up to 250 C.) or sublimed (p about 10.sup.6 mbar, T 300-400 C.) under high vacuum. Yield: 12.1 g (6.2 mmol), 62%. Purity: >99.9% by HPLC.

[0513] It is possible to prepare the following complexes:

TABLE-US-00065 Ligand Variant Temperature Reaction time Ex. Ir complex Extractant Yield Ir(L1001) [01616] L1001 A 250 C. 2 h acetonitrile 65% Ir(L1002) [01617] L1002 A 250 C. 2.5 h acetonitrile/ethyl acetate 1:1 70% Ir(L1003) [01618] L1003 A 250 C. 3 h toluene/heptane 1:1 80% Ir(L1004) [01619] L1004 A 250 C. 3 h toluene 68% Ir(L1005) [01620] L1005 A 250 C. 4 h toluene 75% Ir(L1006) [01621] L1006 A 250 C. 3 h ethyl acetate 74% Ir(L1007) [01622] L1007 A 250 C. 2 h ethyl acetate/ acetonitrile 1:1 66% Ir(L1008) [01623] L1008 A 250 C. 3 h toluene 67% Ir(L1009) [01624] L1009 A 250 C. 2 h toluene 60% Ir(L1010) [01625] L1010 A 250 C. 4 h toluene 58% Ir(L1011) [01626] L1011 A 250 C. 4 h toluene 59% Ir(L1012) [01627] L1012 A 250 C. 2 h o-xylene 80% Ir(L1013) [01628] L1013 A 250 C. 2 h toluene 76% Ir(L1014) [01629] L1014 A 250 C. 3 h toluene 50% Ir(L1015) [01630] L1015 A 250 C. 3 h ethyl acetate 53% Ir(L1016) [01631] L1016 A 250 C. 2 h toluene 70% Ir(L1017) [01632] L1017 A 250 C. 2 h ethyl acetate 65% Ir(L1018) [01633] L1018 A 250 C. 2 h ethyl acetate 69% Ir(L1019) [01634] L1019 A 250 C. 3 h cyclohexane 72% Ir(L1020) [01635] L1020 A 250 C. 2 h toluene 14% Ir(L1021) [01636] L1021 A 250 C. 2 h toluene/heptane 1:1 68% Ir(L1022) [01637] L1022 A 250 C. 3 h ethyl acetate 60% Ir(L1023) [01638] L1023 A 250 C. 2 h ethyl acetate 58% Ir(L1024) [01639] L1024 A 250 C. 4 h acetonitrile 64% Ir(L1025) [01640] L1025 A 250 C. 3 h ethyl acetate 66% Ir(L1026) [01641] L1026 A 250 C. 5 h acetonitrile 62% Ir(L1027) [01642] L1027 A 250 C. 5 h acetonitrile 16% Ir(L1028) [01643] L1028 A 250 C. 2 h cyclohexane 75% Ir(L1029) [01644] L1029 A 250 C. 2 h ethyl acetate 80% Ir(L1030) [01645] L1030 A 250 C. 3 h ethyl acetate/ acetonitrile 1:1 55% Ir(L1031) [01646] L1031 A 250 C. 3 h chromatography 53% Ir(L1032) [01647] L1032 A 250 C. 3 h toluene 74% Ir(L1033) [01648] L1033 A 250 C. 4 h toluene 70% Ir(L1034) [01649] L1034 A 250 C. 2 h ethyl acetate 63% Ir(L1035) [01650] L1035 A 250 C. 4 h toluene 55% Ir(L1036) [01651] L1036 A 250 C. 2 h toluene 60% Ir(L1037) [01652] L1037 A 225 C. 10 h toluene 45%

G. Functionalization of the Metal ComplexesPart 2

[0514] 1) Halogenation of the Metal Complexes:

[0515] To a solution or suspension of 10 mmol of a complex bearing AC-H groups (with A=1, 2, 3) in the para position to the iridium in 500 ml to 2000 ml of dichloromethane according to the solubility of the metal complexes is added, in the dark and with exclusion of air, at 30 to +30 C., A10.5 mmol of N-halosuccinimide (halogen: CI, Br, I), and the mixture is stirred for 20 h. Complexes of sparing solubility in DCM may also be converted in other solvents (TCE, THF, DMF, etc.) and at elevated temperature. Subsequently, the solvent is substantially removed under reduced pressure. The residue is extracted by boiling with 100 ml of methanol, and the solids are filtered off with suction, washed three times with 30 ml of methanol and then dried under reduced pressure. This gives the iridium complexes brominated in the para position to the iridium.

[0516] Substoichiometric brominations, for example mono- and dibrominations of complexes having 3 CH groups in the para position to iridium, usually proceed less selectively than the stoichiometric brominations. The crude products of these brominations can be separated by chromatography (CombiFlash Torrent from A. Semrau).

Example Ir(L1000-3Br)

[0517] ##STR01653##

[0518] To a suspension, stirred at 0 C., of 24.7 g (15.0 mmol) of Ir(L1000) in 2000 ml of DCM are added 8.8 g (49.5 mmol) of N-bromosuccinimide all at once, and also 0.1 ml of 47% hydrobromic acid, and the mixture is stirred at 0 C. for 2 h and then at room temperature for a further 20 h. After removing about 1900 ml of the DCM under reduced pressure, 150 ml of methanol are added to the red suspension, and the solids are filtered off with suction, washed three times with about 50 ml of methanol and then dried under reduced pressure. Yield: 25.5 g (13.5 mmol), 90%; purity: >99.0% by .sup.1H NMR.

[0519] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00066 Ex. Reactant Ir complex Yield Ir(L1001-3Br) Ir(L1001) [01654] 81% Ir(L1002-3Br) Ir(L1002) [01655] 80% Ir(L1003-3Br) Ir(L1003) [01656] 86% Ir(L1004-3Br) Ir(L1004) [01657] 72% Ir(L1005-3Br) Ir(L1005) [01658] 79% Ir(L1006-3Br) Ir(L1006) [01659] 77% Ir(L1007-3Br) Ir(L1007) [01660] 84% Ir(L1008-3Br) Ir(L1008) [01661] 89% Ir(L1009-3Br) Ir(L1009) [01662] 85% Ir(L1010-3Br) Ir(L1010) [01663] 78% Ir(L1011-3Br) Ir(L1011) [01664] 81% Ir(L1012-3Br) Ir(L1012) [01665] 94% Ir(L1013-3Br) Ir(L1013) [01666] 96% Ir(L1014-3Br) Ir(L1014) [01667] 71% Ir(L1015-3Br) Ir(L1015) [01668] 75% Ir(L1016-3Br) Ir(L1016) [01669] 90% Ir(L1017-3Br) Ir(L1017) [01670] 82% Ir(L1018-3Br) Ir(L1018) [01671] 80% Ir(L1019-3Br) Ir(L1019) [01672] 80% Ir(L1020-3Br) Ir(L1020) [01673] 85% Ir(L1021-3Br) Ir(L1021) [01674] 87% Ir(L1022-3Br) Ir(L1022) [01675] 93% Ir(L1023-3Br) Ir(L1023) [01676] 90% Ir(L1024-3Br) Ir(L1024) [01677] 82% Ir(L1025-3Br) Ir(L1025) [01678] 88% Ir(L1026-3Br) Ir(L1026) [01679] 76% Ir(L1027-3Br) Ir(L1027) [01680] 78% Ir(L1028-3Br) Ir(L1028) [01681] 85% Ir(L1029-3Br) Ir(L1029) [01682] 95% Ir(L1030-3Br) Ir(L1030) [01683] 91% Ir(L1031-3Br) Ir(L1031) [01684] 85% Ir(L1032-3Br) Ir(L1032) [01685] 88% Ir(L1033-3Br) Ir(L1033) [01686] 84%

2) Suzuki Coupling with the Brominated Iridium Complexes. Variant a, Biphasic Reaction Mixture

[0520] To a suspension of 10 mmol of a brominated complex, 12-30 mmol of boronic acid or boronic ester per Br function and 60-100 mmol of tripotassium phosphate in a mixture of 300 ml of toluene, 150 ml of ethanol and 150 ml of water are added 0.6 mmol of tri-ortho-tolylphosphine and then 0.1 mmol of palladium(II) acetate, and the mixture is heated under reflux for 24 h. After cooling, 500 ml of water and 200 ml of toluene are added, the aqueous phase is removed, and the organic phase is washed three times with 200 ml of water and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulphate. The mixture is filtered through a Celite bed and washed through with toluene, the toluene is removed almost completely under reduced pressure, 300 ml of methanol are added, and the precipitated crude product is filtered off with suction, washed three times with 50 ml each time of methanol and dried under reduced pressure. The crude product is columned on silica gel. The metal complex is finally heat-treated or sublimed. The heat treatment is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 200-300 C. The sublimation is effected under high vacuum (p about 10.sup.6 mbar) within the temperature range of about 300-400 C., the sublimation preferably being conducted in the form of a fractional sublimation.

[0521] Variant B, Monophasic Reaction Mixture:

[0522] To a suspension of 10 mmol of a brominated complex, 12-30 mmol of boronic acid or boronic ester per Br function and 60-100 mmol of the base (potassium fluoride, tripotassium phosphate (anhydrous or monohydrate or trihydrate), potassium carbonate, caesium carbonate etc.) and 100 g of glass beads (diameter 3 mm) in 100 ml-500 ml of an aprotic solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.) are added 0.6 mmol of tri-ortho-tolylphosphine and then 0.1 mmol of palladium(II) acetate, and the mixture is heated under reflux for 24 h. Alternatively, it is possible to use other phosphines such as tri-tert-butylphosphine, S-Phos, X-Phos, RuPhos, XanthPhos, etc., the preferred phosphine:palladium ratio in the case of these phosphines being 2:1 to 1.2:1. The solvent is removed under reduced pressure, the product is taken up in a suitable solvent (toluene, dichloromethane, ethyl acetate, etc.) and purification is effected as described in Variant A.

[0523] Synthesis of Ir1000:

##STR01687##

[0524] Variant A:

[0525] Use of 18.9 g (10.0 mmol) of Ir(L1000-3Br) and 9.8 g (80.0 mmol) of phenylboronic acid [98-80-6], 19.1 g (90 mmol) of tripotassium phosphate (anhydrous), 183 mg (0.6 mmol) of tri-o-tolylphosphine [6163-58-2], 23 mg (0.1 mmol) of palladium(II)acetate, 300 ml of toluene, 150 ml of ethanol and 150 ml of water, reflux, 24 h. Chromatographic separation twice on silica gel with toluene, followed by hot extraction five times with ethyl acetate. Yield: 9.8 g (5.2 mmol), 52%; purity: about 99.9% by H PLC.

[0526] In an analogous manner, it is possible to prepare the following complexes:

TABLE-US-00067 Reactant Variant/ reaction conditions Boronic acid Ex. Hot extractant Ir complex Yield Ir1001 [01688] [01689] 50% Ir1002 [01690] [01691] 42% Ir1003 [01692] [01693] 56% Ir1004 [01694] [01695] 45% Ir1005 [01696] [01697] 20% Ir1006 [01698] [01699] 39% Ir1007 [01700] [01701] 52% Ir1008 [01702] [01703] 44% Ir1009 [01704] [01705] 55% Ir1010 [01706] [01707] 35% Ir1011 [01708] [01709] 41% Ir1012 [01710] [01711] 56% Ir1013 [01712] [01713] 60% Ir1014 [01714] [01715] 58% Ir1015 [01716] [01717] 60% Ir1016 [01718] [01719] 55% Ir1017 [01720] [01721] 56% Ir1018 [01722] [01723] 61% Ir1019 [01724] [01725] 55% Ir1020 [01726] [01727] 50% Ir1021 [01728] [01729] 28% Ir1022 [01730] [01731] 16% Ir1023 [01732] [01733] 20% Ir1024 [01734] [01735] 60% Ir1025 [01736] [01737] 50% Ir1026 [01738] [01739] 41% Ir1027 [01740] [01741] 71% Ir1028 [01742] [01743] 14% Ir1030 [01744] [01745] 45% Ir1031 [01746] [01747] 61% Ir1032 [01748] [01749] 27% Ir1033 [01750] [01751] 50% Ir1034 [01752] [01753] 40% Ir1035 [01754] [01755] 50% Ir1036 [01756] [01757] 67% Ir1037 [01758] [01759] 70% Ir1038 [01760] [01761] 40% Ir1039 [01762] [01763] 61% Ir1040 [01764] [01765] 88% Ir1041 [01766] [01767] 38%

H: Synthesis of Unsymmetric Ligands

1st Variant

Example S1200 and S1201: Suzuki Coupling with Subsequent Chromatographic Separation

[0527] ##STR01768##

[0528] Into a 2 l four-neck flask with reflux condenser, argon blanketing, precision glass stirrer and internal thermometer are weighed 50 g of 1,3,5-tris(2-bromophenyl)benzene (92.1 mmol) [380626-56-2], 51.8 g of 2-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]pyridine (184.2 mmol) [908350-80-1] and 84.0 g of caesium fluoride (553 mmol), the flask is inertized with argon and then 1000 ml of diethylene glycol dimethyl ether and 100 g of glass beads (diameter 3 mm) are added. The reaction mixture is inertized with argon for 15 min, then 3.2 g of bis(triphenylphosphine)palladium(II) chloride (4.6 mmol) [13965-03-2] are added and the reaction mixture is stirred at internal temperature 130 C. overnight. After cooling, the solvent is substantially removed by rotary evaporation on a rotary evaporator at about 10 mbar and bath temperature 80 C. and the residue is worked up by extraction with 500 ml of toluene and 500 ml of water in a separating funnel. The aqueous phase is extracted once with 200 ml of toluene, then the combined organic phases are washed once with 300 ml of water and once with 150 ml of saturated sodium chloride solution and dried over sodium sulphate, and the solvent is removed under reduced pressure. The residue is chromatographed on silica gel. Gradient elution: eluent:toluene 98%/ethyl acetate 2%. Yield: monosubstituted product S1200: 11.9 g (19.3 mmol), 21% as yellow solid. Purity 95% by 1H NMR. Yield: disubstituted product S1201: 21.7 g (31.3 mmol), 34% as brown solid. Purity 95% by 1H NMR.

[0529] In an analogous manner, it is possible to prepare the following synthons:

TABLE-US-00068 Product Ex. Boronic acid/ester Yield S1204/ S1205 [01769] 18%/ 32% S1206/ S1207 [01770] 15%/ 28%

2nd Cariant

Example S1202: Silylation of 1,3,5-tris(2-bromophenyl)benzene

[0530] ##STR01771##

[0531] In a 2 I four-neck flask with precision glass stirrer, internal thermometer and argon blanketing, 50 g of 1,3,5-tris(2-bromophenyl)benzene (92.1 mmol) [380626-56-2] are dissolved in 1000 ml of dry THF and cooled down to 78 C. in an acetone/dry ice bath. Then 92.1 ml of a 2.5 mol/l solution of n-butyllithium (230.3 mmol) in n-hexane [109-72-8] are added dropwise in such a way that the internal temperature does not exceed 65 C. The mixture is stirred at this temperature for a further 1 h. Subsequently, 30.5 ml of chlorotrimethylsilane (239.5 mmol) [75-77-4] in 300 ml of dry THF are rapidly added dropwise via a dropping funnel, the reaction mixture is stirred at 78 C. for another 1 h and then allowed to thaw gradually to room temperature overnight. 20 ml of methanol are slowly added dropwise. Subsequently, the reaction mixture is transferred into a separating funnel and worked up by extraction with 1000 ml of ethyl acetate and 1000 ml of water. The aqueous phase is extracted once more with 500 ml of ethyl acetate, and the combined organic phases are washed with 500 ml of water and 250 ml of saturated sodium chloride solution, dried over sodium sulphate and concentrated to dryness by rotary evaporation. A yellow oil is obtained, which is converted in the next stage without further purification. Yield: 43.1 g, of which by NMR about 60% is product with 2-fold TMS substitution and about 40% product with 3-fold TMS substitution.

Example S1203: Suzuki Coupling of the Silylated Bromophenylbenzene

[0532] ##STR01772##

[0533] Into a 1 l four-neck flask with reflux condenser, precision glass stirrer, heating bath and argon connection are weighed 40.0 g (of which 24 mmol is [2-[3-(2-bromophenyl)-5-(2-trimethylsilylphenyl)phenyl]phenyl]trimethylsilane) of S1202, 16.2 g of 2-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]pyridine (57.6 mmol) [908350-80-1], 7.6 g (72 mmol) of sodium carbonate, 567 mg (2.2 mmol) of triphenylphosphine [603-35-0] and 162 mg (0.72 mmol) of palladium(II) acetate [3375-31-3], and 200 ml of toluene, 100 ml of ethanol and 100 ml of water are added. The reaction mixture is inertized with argon and stirred under reflux for 24 hours. After cooling, the organic phase is removed, the aqueous phase is extracted once with 100 ml of toluene, and the combined organic phases are washed once with 200 ml of water and once with 100 ml of saturated sodium chloride solution and dried over sodium sulphate and concentrated to 50 ml on a rotary evaporator. The resulting solution is chromatographed on silica gel. Gradient elution eluent:heptane>heptane/dichloromethane 1:1. The product fractions are concentrated by rotary evaporation, 100 ml of n-heptane are added to the pink oil obtained and the mixture is stirred at room temperature overnight. The precipitated solid is filtered off with suction and washed twice with 20 ml of n-heptane. A white solid is obtained. Yield: 11.6 g (19.2 mmol), 80%; purity: 98% by .sup.1H NMR.

Example S1200: Bromination of S1203

[0534] ##STR01773##

[0535] In a 500 ml 2-neck flask having a magnetic stirrer bar and argon blanketing, 11.5 g of S1203 (19.0 mmol) are dissolved in 180 ml of dichloromethane and cooled to 0 C. in an ice/water bath. In a dropping funnel, 2.5 ml of bromine (49.4 mmol) are mixed with 100 ml of dichloromethane and then slowly added dropwise. After the addition has ended, the ice/water bath is removed and the reaction mixture is stirred at room temperature for a further 6 h. Then 20 ml of saturated sodium sulphite solution are added dropwise, 50 ml of saturated sodium hydrogencarbonate solution and 3 ml of 20% (w/w) sodium hydroxide solution. The reaction mixture is transferred into a separating funnel, and the organic phase is removed and washed 5 with 100 ml of water and twice with 50 ml of saturated sodium chloride solution, dried over sodium sulphate and concentrated under reduced pressure. A yellow solid is obtained. Yield: 9.4 g (15.2 mmol), 80%; purity 95% by .sup.1H NMR.

Example L1200: Synthesis of the Ligands

[0536] ##STR01774##

[0537] Into a 1 l four-neck flask with reflux condenser, argon blanketing, precision glass stirrer and internal thermometer are weighed 10 g of S1200 (16.2 mmol), 19.9 g of S1100 (38.9 mmol) and 14.8 g of caesium fluoride (97 mmol), the flask is inertized with argon and then 500 ml of diethylene glycol dimethyl ether and 50 g of glass beads (diameter 3 mm) are added. The reaction mixture is inertized under an argon atmosphere for 15 min, then 569 mg of bis(triphenylphosphine)palladium(II) chloride (0.81 mmol) [13965-03-2] are added and the reaction mixture is stirred at internal temperature 130 C. overnight. After cooling, the solvent is substantially removed by rotary evaporation on a rotary evaporator at about 10 mbar and bath temperature 80 C. and the residue is worked up by extraction with 200 ml of toluene and 300 ml of water in a separating funnel. The aqueous phase is extracted once with 100 ml of toluene, then the combined organic phases are washed once with 200 ml of water and once with 100 ml of saturated sodium chloride solution and dried over sodium sulphate, and the solvent is removed under reduced pressure. The residue is chromatographed on silica gel. Gradient elution: eluent: heptane/ethyl acetate 4:1>heptane/ethyl acetate 3:1. A white solid is obtained. 13.5 g (11.0 mmol), 68%, purity 97% by .sup.1H NMR.

[0538] In an analogous manner, it is possible to synthesize the following ligands:

TABLE-US-00069 Ex. Product/synthon/purification Yield L1202 [01775] 70% L1204 [01776] 55%

Example L1201: Synthesis of the Ligands am

[0539] ##STR01777##

[0540] Into a 1 l four-neck flask with reflux condenser, argon blanketing, precision glass stirrer and internal thermometer are weighed 10 g of S1201 (14.5 mmol), 8.9 g of S1100 (17.3 mmol) and 13.2 g of caesium fluoride (87 mmol), the flask is inertized with argon and then 400 ml of diethylene glycol dimethyl ether and 50 g of glass beads (diameter 3 mm) are added. The reaction mixture is inertized under an argon atmosphere for 15 min, then 509 mg of bis(triphenylphosphine)palladium(II) chloride (0.73 mmol) [13965-03-2] are added and the reaction mixture is stirred at internal temperature 130 C. overnight. After cooling, the solvent is substantially removed by rotary evaporation on a rotary evaporator at about 10 mbar and bath temperature 80 C. and the residue is worked up by extraction with 200 ml of toluene and 300 ml of water in a separating funnel. The aqueous phase is extracted once with 100 ml of toluene, then the combined organic phases are washed once with 200 ml of water and once with 100 ml of saturated sodium chloride solution and dried over sodium sulphate, and the solvent is removed under reduced pressure. The residue is chromatographed on silica gel. Gradient elution: eluent:dichloromethane>dichloromethane/ethyl acetate 95:5. The yellow solid obtained is recrystallized from 60 ml of ethyl acetate at reflux. A white solid is obtained. 10.7 g (10.7 mmol), 74%, purity 99% by .sup.1H NMR.

[0541] In an analogous manner, it is possible to synthesize the following ligands:

TABLE-US-00070 Ex. Product/synthon/purification Yield L1203 [01778] 65% L1205 [01779] 58%

I: Synthesis of the Metal ComplexesPart 3

Example Ir(L1200)

[0542] ##STR01780##

[0543] Procedure analogous to that described in the synthesis of Ir(L1000) (see B. Synthesis of the metal complexes, Variant A). The crude product is columned on silica gel with toluene as eluent. The crude product is purified further by continuous hot extraction five times with ethyl acetate/acetonitrile 1:1 (extractant, amount initially charged in each case about 150 ml, extraction thimble: standard Soxhlet thimbles made from cellulose from Whatman) with careful exclusion of air and light. Finally, the product is heat-treated (p about 10.sup.6 mbar, T up to 250 C.) or sublimed (p about 10.sup.6 mbar, T 300-400 C.) under high vacuum. A red solid is obtained. Yield: 8.5 g (6.0 mmol), 60%. Purity: >99.9% by HPLC.

[0544] In an analogous manner, it is possible to prepare the following complexes:

TABLE-US-00071 Ligand Variant Temperature Reaction time Ex. Ir complex Extractant Yield Ir(L1201) [01781] L1201 A 250 C. 2 h cyclohexane 60% Ir(L1202) [01782] L1202 A 250 C. 2.5 h acetonitrile/ ethyl acetate 1:1 40% Ir(L1204) [01783] L1204 A 250 C. 2 h cyclohexane 54% Ir(L1203) [01784] L1203 A 250 C. 3 h cyclohexane 14% Ir(L1205) [01785] L1205 A 250 C. 2 h ethyl acetate 16%

Example A: Thermal and Photophysical Properties and Oxidation and Reduction Potentials

[0545] Table 1 collates the thermal and photochemical properties and oxidation and reduction potentials of the comparative materials IrPPy, Ir1 to 4 (for structures see Table 13) and the selected materials of the invention. The compounds of the invention have improved thermal stability and photostability compared to the materials according to the prior art. While materials according to the prior art exhibit brown discolouration and ashing after thermal storage at 380 C. for 7 days and secondary components in the region of >2 mol % can be detected in the .sup.1H NMR, the complexes of the invention are inert under these conditions. This thermal robustness is crucial especially for the processing of the materials under high vacuum (vapour small-molecule devices). In addition, the compounds of the invention have very good photostability in anhydrous C.sub.6D.sub.6 solution under irradiation with light of wavelength about 455 nm. More particularly, in contrast to prior art complexes containing bidentate ligands, no facial-meridional isomerization is detectable in the .sup.1H NMR. As can be inferred from Table 1, the compounds of the invention in solution show universally very high PL quantum efficiencies.

TABLE-US-00072 TABLE 1 Therm. stab. PL-max. HOMO Complex Photo. stab. FWHM PLQE LUMO Comparative examples, for structures see Table 13 IrPPy decomposition 509 0.97 decomposition 67 toluene Ir1 513 0.97 5.09 60 toluene 1.99 Ir2 decomposition 516 0.97 5.05 decomposition 69 toluene 1.71 Ir3 decomposition 510* 0.76* decomposition BuCN Ir4 decomposition 524* 0.79* decomposition MeCN Ir6 decomposition 595 0.82 5.18 decomposition 63 toluene 2.70 Inventive examples Ir(L1) 545 1.00 4.84 66 toluene 1.99 Ir(L2) no decomp. 530 0.98 5.07 no decomp. 66 toluene 2.12 0.93 MeCN Ir(L14) no decomp. 522 1.00 5.02 no decomp. 64 toluene 1.98 Ir(L34) 586 0.75 4.89 86 toluene 2.42 Ir(L48) no decomp. 535 0.94 5.06 no decomp. 70 toluene 2.11 Ir(L71) no decomp. 543 0.98 no decomp. 74 toluene Ir(L72) no decomp. 520 0.97 5.07 no decomp. 64 toluene 1.99 Ir(L97) no decomp. 520 0.74 no decomp. 73 THF Ir(L98) no decomp. 505 0.94 no decomp. 38 toluene Ir(L111) no decomp. 519 0.99 4.99 no decomp. 61 toluene 1.94 Ir(L112) 527 0.91 71 DCM Ir(L114) 497, 536 0.77 5.05 32 toluene Ir(L200) no decomp. 523 0.97 5.03 no decomp. 60 toluene 2.01 Ir(L204) 526 0.94 65 toluene Ir(L200) no decomp. 523 0.97 5.03 no decomp. 60 toluene 2.01 Ir(L220) no decomp. 523 0.97 no decomp. 60 toluene Ir101 526 0.97 62 toluene Ir109 535 0.96 5.09 65 toluene 2.19 Ir110 520 0.97 5.07 56 toluene 2.06 Ir111 519 0.96 60 toluene Ir112 517 0.97 57 toluene Ir113 519 0.94 64 DCM Ir114 524 0.97 59 toluene Ir115 518 0.95 56 DCM Ir116 no decomp. 520 0.97 5.01 no decomp. 55 toluene 1.91 Ir117 no decomp. 515 0.98 no decomp. 55 toluene Ir118 no decomp. 516 0.98 no decomp. 55 toluene Ir119 522 0.97 59 toluene Ir120 523 0.95 56 toluene Ir121 519 0.97 56 toluene Ir122 524 0.95 58 toluene Ir123 519 0.97 5.08 54 toluene 2.01 Ir124 524 0.99 55 toluene Ir126 519 0.99 5.04 51 toluene 1.97 Ir146 no decomp. 523 0.98 5.02 no decomp. 56 toluene 2.02 Ir301 no decomp. 523 0.98 no decomp. 68 toluene Ir303 no decomp. 505 0.89 5.56 no decomp. 64 toluene 2.41 Ir305 no decomp. 491, 526 toluene no decomp. 52 0.99 Ir309 no decomp. 506 toluene 5.29 no decomp. 59 0.98 2.25 Ir405 507 toluene 59 0.93 Ir700 522 0.96 5.02 63 toluene 2.02 Ir(L1000) no decomp. 604 0.84 5.21 50 toluene Ir(L1001) no decomp. 599 0.88 5.17 47 toluene 2.70 Ir(L1009) no decomp. 609 0.83 54 toluene Ir(L1036) no decomp. 593 0.84 47 toluene Ir1000 no decomp. 609 0.90 46 toluene Ir1001 no decomp. 605 0.90 45 toluene Ir1002 no decomp. 613 0.85 5.18 48 toluene 2.83 Ir1003 no decomp. 604 0.91 47 toluene Ir1004 no decomp. 610 51 Ir1005 no decomp. 618 55 Ir1006 no decomp. 615 51 Ir1007 no decomp. 615 50 Ir(L1200) no decomp. 618 77 Ir(L1201) no decomp. 626 0.67 86 toluene *Data from G. St-Pierre et al., Dalton Trans, 2011, 40, 11726. Legend: Therm. stab. (thermal stability): Storage in ampoules closed by fusion under reduced pressure, 7 days at 380 C. Visual assessment for colour change/brown discolouration/ashing and analysis by means of .sup.1H NMR spectroscopy. Photo. stab. (photochemical stability): Irradiation of about 1 mmolar solutions in anhydrous C.sub.6D.sub.6 (degassed NMR tubes closed by fusion) with blue light (about 455 nm, 1.2 W Lumispot from Dialight Corporation, USA) at RT. PL-max.: Maximum of the PL spectrum in [nm] of a degassed about 10.sup.5 molar solution at RT, excitation wavelength 370 nm, for solvent see PLQE column. FWHM: Half-height width of the PL spectrum in [nm] at RT. PLQE.: Abs. photoluminescence quantum efficiency of a degassed about. 10.sup.5 molar solution in the solvent specified at RT. HOMO, LUMO: in [eV] vs. vacuum, determined in dichloromethane solution (oxidation) or THF (reduction) with internal ferrocene reference (4.8 eV vs. vacuum).

Example B: Comparison of the Synthesis Yields of Ir(L2) Vs. Ir3 and Ir(L72) vs. Ir4

[0546] Compound Ir(L2) of the invention is obtained under identical synthesis conditions (Variant C*) in a much better yield (79%) than the compound according to the prior art Ir3 (33%). The same applies to Ir(L72) at 68% vs. Ir4 at 37%. Yields for Ir3 and Ir4: see G. St-Pierre et al., Dalton Trans, 2011, 40, 11726.

Example C: Solubility of Selected Complexes at 25 C.

[0547] For the processing of the complexes of the invention from solution (spin-coating, inkjet printing, nozzle printing, bar coating, etc.), solutions of prolonged stability having solids contents of about 5 mg/ml or more are required.

TABLE-US-00073 TABLE 2 Solubilities of selected complexes Complex Solvent Solubility Ir(L1) toluene >5 mg/ml Ir(L64) anisole >5 mg/ml Ir(L118) toluene >10 mg/ml Ir(L39) 3-phenoxytoluene >5 mg/ml Ir(L49) 3-phenoxytoluene >10 mg/ml Ir(L53) toluene >10 mg/ml Ir(L280) toluene >10 mg/ml Ir101 3-phenoxytoluene >10 mg/ml Ir104 toluene >20 mg/ml Ir105 3-phenoxytoluene >15 mg/ml Ir108 3-phenoxytoluene >15 mg/ml Ir113 3-phenoxytoluene >15 mg/ml Ir116 toluene >5 mg/ml Ir126 o-xylene >25 mg/ml Ir127 o-xylene >50 mg/ml Ir132 3-phenoxytoluene >50 mg/ml Ir151 3-phenoxytoluene >30 mg/ml Ir152 3-phenoxytoluene >30 mg/ml Ir308 3-phenoxytoluene >20 mg/ml Ir700 3-phenoxytoluene >50 mg/ml Ir1019 3-phenoxytoluene >10 mg/ml Ir1038 3-phenoxytoluene >10 mg/ml

Example: Production of the OLEDs

[0548] 1) Vacuum-Processed Devices:

[0549] OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 2004/058911, which is adapted to the circumstances described here (variation in layer thickness, materials used).

[0550] In the examples which follow, the results for various OLEDs are presented. Glass plaques with structured ITO (50 nm, indium tin oxide) form the substrates to which the OLEDs are applied. The OLEDs basically have the following layer structure: substrate/hole transport layer 1 (HTL1) consisting of HTM doped with 5% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 2 (HTL2)/optional electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm.

[0551] First of all, vacuum-processed OLEDs are described. For this purpose, all the materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as M3:M2:Ir(L2) (55%:35%:10%) mean here that the material M3 is present in the layer in a proportion by volume of 55%, M2 in a proportion of 35% and Ir(L2) in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLEDs can be found in Table 2. The materials used for production of the OLEDs are shown in Table 13.

[0552] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the power efficiency (measured in cd/A) and the voltage (measured at 1000 cd/m.sup.2 in V) are determined from current-voltage-brightness characteristics (IUL characteristics). For selected experiments, the lifetime is determined. The lifetime is defined as the time after which the luminance has fallen from a particular starting luminance to a certain proportion. The figure LD50 means that the lifetime specified is the time at which the luminance has dropped to 50% of the starting luminance, i.e. from, for example, 1000 cd/m.sup.2 to 500 cd/m.sup.2. According to the emission colour, different starting brightnesses are selected. The values for the lifetime can be converted to a figure for other starting luminances with the aid of conversion formulae known to those skilled in the art. In this context, the lifetime for a starting luminance of 1000 cd/m.sup.2 is a standard figure.

[0553] Use of Compounds of the Invention as Emitter Materials in Phosphorescent OLEDs

[0554] One use of the compounds of the invention is as phosphorescent emitter materials in the emission layer in OLEDs. The iridium compounds according to Table 13 are used as a comparison according to the prior art. The results for the OLEDs are collated in Table 4.

TABLE-US-00074 TABLE 3 Structure of the OLEDs HTL2 EBL EML HBL ETL thick- thick- thick- thick- thick- Ex. ness ness ness ness ness Green OLEDs Ref.-D1 HTM M1:IrPPy ETM1:ETM2 40 nm (90%:10%) (50%:50%) 30 nm 30 nm Ref.-D2 HTM M1:IrPPy HBM1 ETM1:ETM2 40 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm Ref.-D3 HTM M1:IrPPy HBM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm Ref.-D4 HTM M1:Ir2 ETM1:ETM2 40 nm (90%:10%) (50%:50%) 30 nm 30 nm Ref.-D5 HTM M1:Ir2 HBM1 ETM1:ETM2 40 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm Ref.-D6 HTM M1:Ir2 HBM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm Ref.-D7 HTM M1:M3:Ir2 HBM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm Ref.-D8 HTM M1:Ir3 HBM1 ETM1:ETM2 40 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm D1 HTM M1:Ir(L2) ETM1:ETM2 40 nm (90%:10%) (50%:50%) 30 nm 30 nm D2 HTM M1:Ir(L2) HBM1 ETM1:ETM2 40 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm D3 HTM M1:Ir(L2) HBM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D4 HTM M2:Ir(L2) HBM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D5 HTM M1:M3:Ir(L2) HBM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D6 HTM M1:M3:Ir(L14) HBM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm

TABLE-US-00075 TABLE 4 Results for the vacuum-processed OLEDs Ex. EQE (%) Voltage (V) CIE x/y LD50 (h) 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Green OLEDs Ref.-D1 15.8 2.7 0.33/062 55000 Ref.-D2 15.6 3.3 0.33/062 70000 Ref.-D3 16.0 3.3 0.33/062 85000 Ref.-D4 17.4 2.5 0.35/0.61 160000 Ref.-D5 17.3 3.2 0.35/0.61 210000 Ref.-D6 17.7 3.2 0.35/0.62 240000 Ref.-D7 17.6 3.1 0.35/0.62 340000 Ref.-D8 17.8 3.2 0.34/0.62 180000 D1 17.8 2.6 0.40/0.59 320000 D2 18.1 3.0 0.40/0.59 360000 D3 18.3 2.9 0.40/0.58 430000 D4 19.7 3.0 0.40/0.59 450000 D5 19.2 3.0 0.40/0.59 480000 D6 20.3 3.1 0.37/0.61 570000

[0555] 2) Further Vacuum-Processed Components

[0556] Examples D7 to D84 and Ref-D9 and Ref-D14 which follow (see Tables 5 and 6) present data of further OLEDs. Processing is effected as described in 1), except that other substrates described hereinafter are used: Cleaned glass plaques (cleaning in Miele laboratory glass washer, Merck Extran detergent) coated with structured ITO (indium tin oxide) of thickness 50 nm are pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator from UVP) and, within 30 min, for improved processing, coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulphonate), purchased as CLEVIOS P VP AI 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution) and then baked at 180 C. for 10 min. These coated glass plaques form the substrates to which the OLEDs are applied.

[0557] In Examples D27, D28, Ref-D13 and Ref-D14, rather than the 20 nm-thick HTM layer doped with 5% NDP-9, a 20 nm-thick HTM2 layer doped with 5% NDP-9 is used.

[0558] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in Im/W) and the external quantum efficiency (EQE, measured in percent) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics, and also the lifetime are determined. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The parameter U1000 in Table 6 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2.

[0559] The lifetime LT80 is defined as the time after which the luminance drops to 80% of the starting luminance in the course of operation with a constant current of 40 mA/cm.sup.2.

TABLE-US-00076 TABLE 5 Construction of the further vacuum-processed OLEDs HTL2 EBL EML HBL ETL thick- thick- thick- thick- thick- Ex. ness ness ness ness ness D7 HTM M1:Ir116 ETM1 ETM1:ETM2 40 nm (95%:5%) 10 nm (50%:50%) 30 nm 30 nm D8 HTM M1:Ir116 ETM1 ETM1:ETM2 40 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm D9 HTM M1:Ir116 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D10 HTM M1:Ir116 ETM1 ETM1:ETM2 40 nm (80%:20%) 10 nm (50%:50%) 30 nm 30 nm D11 HTM M1:M3:Ir116 ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D12 HTM M1:M3:Ir116 ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D13 HTM M6:Ir116 ETM1 ETM1:ETM2 40 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm D14 HTM M6:Ir116 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D15 HTM M1:Ir(L111) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D16 HTM M6:Ir(L111) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D17 HTM M1:M3:Ir(L111) ETM1 ETM1:ETM2 40 nm (40%:40%:20%) 10 nm (50%:50%) 30 nm 30 nm D18 HTM M1:Ir(L48) ETM1 ETM1:ETM2 40 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm D19 HTM M1:Ir(L48) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D20 HTM M1:Ir(L48) ETM1 ETM1:ETM2 40 nm (80%:20%) 10 nm (50%:50%) 30 nm 30 nm D21 HTM M1:M3:Ir(L48) ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D22 HTM M1:M3:Ir(L48) ETM1 ETM1:ETM2 40 nm (42.5%:42.5%:15%) 10 nm (50%:50%) 30 nm 30 nm D23 HTM M1:M3:Ir(L48) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D24 HTM M1:M3:Ir(L48) ETM1 ETM1:ETM2 40 nm (30%:60%:10%) 10 nm (50%:50%) 30 nm 30 nm D25 HTM M1:M3:Ir(L48) ETM1 ETM1:ETM2 40 nm (57%:28%:15%) 10 nm (50%:50%) 30 nm 30 nm D26 HTM M7:M3:Ir(L14) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D27 HTM2 M1:M3:Ir(L14) ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D28 HTM2 M1:M3:Ir(L14-D9) ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D29 HTM2 M1:M3:Ir(L14) ETM1 ETM1:ETM2 40 nm (47.5%:47.5%:5%) 10 nm (50%:50%) 30 nm 30 nm D30 HTM M2:M3:Ir(L2) ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D31 HTM M2:M3:Ir(L2) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D32 HTM2 M1:M3:Ir(L3) ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D33 HTM M1:M3:Ir(L20) ETM1 ETM1:ETM2 50 nm (40%:50%:10%) 10 nm (50%:50%) 35 nm 30 nm D34 HTM M1:M3:Ir(L18) ETM1 ETM1:ETM2 50 nm (40%:50%:10%) 10 nm (50%:50%) 35 nm 30 nm D35 HTM M1:M3:Ir(L23) ETM1 ETM1:ETM2 40 nm (40%:45%:15%) 10 nm (50%:50%) 30 nm 30 nm D36 HTM M1:M3:Ir(L117) ETM1 ETM1:ETM2 40 nm (35%:55%:10%) 10 nm (50%:50%) 30 nm 30 nm D37 HTM M6:Ir(L27) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D38 HTM M1:M3:Ir(L51) ETM1 ETM1:ETM2 40 nm (45%:40%:15%) 10 nm (50%:50%) 30 nm 30 nm D39 HTM M1:M3:Ir(L71) ETM1 ETM1:ETM2 40 nm (45%:40%:15%) 10 nm (50%:50%) 35 nm 30 nm D40 HTM M1:M3:Ir(L79) ETM1 ETM1:ETM2 40 nm (20%:60%:20%) 10 nm (50%:50%) 30 nm 30 nm D41 HTM M8:M9:Ir(L88) ETM1 ETM1:ETM2 40 nm (55%:30%15%) 10 nm (50%:50%) 30 nm 30 nm D42 HTM M1:Ir(L112) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D43 HTM M8:Ir(123) ETM1 ETM1:ETM2 30 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D44 HTM M1:Ir(L128) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D45 HTM M8:Ir(L133) ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D46 HTM M1:Ir(L138) ETM1 ETM1:ETM2 50 nm (85%:15%) 5 nm (50%:50%) 40 nm 30 nm D47 HTM M1:M3:Ir(L138) ETM1 ETM1:ETM2 40 nm (42.5%:42.5%:15%) 10 nm (50%:50%) 30 nm 30 nm D48 HTM M1:M9:Ir(L146) ETM1 ETM1:ETM2 40 nm (50%:40%:10%) 10 nm (50%:50%) 30 nm 30 nm D49 HTM M1:M3:Ir(L200) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D50 HTM M1:M3:Ir(L201) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D51 HTM M1:M3:Ir(L202) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D52 HTM M1:M3:Ir(L206) ETM1 ETM1:ETM2 40 nm (50%:35%:15%) 10 nm (50%:50%) 30 nm 30 nm D53 HTM M1:M3:Ir(L204) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D54 HTM M1:M3:Ir(L222) ETM1 ETM1:ETM2 40 nm (40%:45%:15%) 10 nm (50%:50%) 30 nm 30 nm D55 HTM M1:M3:Ir(L255) ETM1 ETM1:ETM2 40 nm (40%:45%:15%) 10 nm (50%:50%) 30 nm 30 nm D56 HTM M1:M3:Ir(L271) ETM1 ETM1:ETM2 40 nm (40%:40%:20%) 10 nm (50%:50%) 30 nm 30 nm D57 HTM Ir116 M1:M9:Ir(L67) ETM1 ETM1:ETM2 30 nm 20 nm (60%:20%:20%) 10 nm (50%:50%) 30 nm 30 nm D58 HTM2 M1:M3:Ir(L274) ETM1 ETM1:ETM2 40 nm (50%:40%:10%) 10 nm (50%:50%) 30 nm 30 nm D59 HTM M1:M3:Ir301 ETM1 ETM1:ETM2 40 nm (40%:45%:15%) 10 nm (50%:50%) 30 nm 30 nm D60 HTM M1:M3:Ir302 ETM1 ETM1:ETM2 40 nm (20%:70%:10%) 10 nm (50%:50%) 30 nm 30 nm D61 HTM M1:M9:Ir305 ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D62 HTM M1:M9:Ir306 ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D63 HTM M1:M3:Ir307 ETM1 ETM1:ETM2 40 nm (40%:45%:15%) 10 nm (50%:50%) 30 nm 30 nm D64 HTM M1:M9:Ir311 ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D65 HTM M1:M9:Ir313 ETM1 ETM1:ETM2 40 nm (60%:25%:15%) 10 nm (50%:50%) 30 nm 30 nm D66 HTM M1:M3:Ir150 ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D67 HTM M1:M3:IrL760-1 ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D68 HTM M1:M3:Ir146 ETM1 ETM1:ETM2 40 nm (45%:40%:15%) 10 nm (50%:50%) 30 nm 30 nm D69 HTM M7:M10:Ir(L25) ETM1 ETM1:ETM2 40 nm (50%:30%:20%) 10 nm (50%:50%) 30 nm 30 nm D70 HTM M1:M3:Ir(L8) ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D71 HTM M1:M3:Ir(L20) ETM1 ETM1:ETM2 40 nm (40%:40%:20%) 10 nm (50%:50%) 30 nm 30 nm D72 HTM2 M1:M3:Ir(L99) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 40 nm 30 nm D73 HTM2 M1:M3:Ir(L101) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D74 HTM M1:M3:Ir(L121) ETM1 ETM1:ETM2 40 nm (55%:30%:15%) 10 nm (50%:50%) 40 nm 30 nm D75 HTM M1:M9:Ir(L145) ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D76 HTM M1:M3:Ir(L82) ETM1 ETM1:ETM2 40 nm (45%:40%:15%) 10 nm (50%:50%) 40 nm 30 nm D77 HTM M1:M3:Ir(L88) ETM1 ETM1:ETM2 40 nm (35%:50%:15%) 10 nm (50%:50%) 30 nm 30 nm D78 HTM M1:M3:Ir(L89) ETM1 ETM1:ETM2 40 nm (35%:50%:15%) 10 nm (50%:50%) 30 nm 30 nm D79 HTM2 M1:M3:Ir(L210) ETM1 ETM1:ETM2 40 nm (55%:30%:15%) 10 nm (50%:50%) 40 nm 30 nm D80 HTM M1:M3:Ir(L233) ETM1 ETM1:ETM2 40 nm (65%:30%:5%) 10 nm (50%:50%) 30 nm 30 nm D81 HTM M1:M3:Ir(L69) ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D82 HTM M6:Ir116 ETM1 M200 40 nm (85%:15%) 10 nm 30 nm 30 nm D83 HTM M6:Ir116 ETM1 M400 40 nm (85%:15%) 10 nm 30 nm 30 nm D84 HTM M1:M3:Ir(L257) ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm Ref-D9 HTM M1:IrPPy ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm Ref-D10 HTM M1:Ir2 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm Ref-D11 HTM M1:M3:IrPPy ETM1 ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm Ref-D12 HTM M1:M3:Ir2 ETM ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm Ref-D13 HTM2 M1:M3:Ir2 ETM ETM1:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm Ref-D14 HTM2 M1:M3:Ir2 ETM1 ETM1:ETM2 40 nm (47.5%:47.5%:5%) 10 nm (50%:50%) 30 nm 30 nm

TABLE-US-00077 TABLE 6 Data of the further vacuum-processed OLEDs Ex. EQE1000 (%) U1000 (V) CIE x/y LT80 (h) D7 20.6 2.9 0.33/0.64 50 D8 20.5 2.9 0.33/0.64 130 D9 20.1 2.9 0.33/0.64 230 D10 19.4 2.9 0.33/0.63 255 D11 20.8 3.0 0.32/0.64 245 D12 21.9 3.0 0.32/0.64 260 D13 22.9 3.0 0.33/0.64 90 D14 21.9 3.0 0.33/0.64 175 D15 15.7 3.2 0.36/0.62 290 D16 17.9 3.1 0.35/0.62 190 D17 17.0 3.4 0.35/0.62 305 D18 17.8 3.0 0.39/0.59 170 D19 17.6 2.9 0.40/0.59 400 D20 17.2 3.1 0.40/0.58 515 D21 20.1 3.2 0.39/0.59 465 D22 19.5 3.1 0.40/0.59 500 D23 20.5 3.1 0.40/0.59 330 D24 18.1 3.3 0.39/0.59 260 D25 19.5 3.0 0.40/0.59 500 D26 19.4 3.8 0.35/0.62 280 D27 20.5 3.2 0.35/0.62 240 D28 20.9 3.2 0.34/0.62 290 D29 19.2 3.3 0.36/0.61 305 D30 19.3 3.3 0.36/0.60 210 D31 20.3 3.1 0.36/0.61 195 D32 20.4 3.3 0.37/0.62 280 D33 19.8 3.2 0.46/0.53 580 D34 18.0 3.2 0.67/0.33 490 D35 21.1 3.3 0.33/0.64 360 D36 20.3 3.3 0.32/0.65 370 D37 19.9 3.2 0.45/0.52 390 D38 20.9 3.1 0.45/0.53 420 D39 19.9 3.2 0.42/0.57 510 D40 20.3 3.3 0.28/0.65 280 D41 18.8 3.3 0.18/0.38 330 D42 17.0 3.2 0.37/0.62 450 D43 20.7 3.5 0.20//0.55 370 D44 18.0 3.1 0.36/0.60 210 D45 18.5 3.3 0.18/0.39 190 D46 17.9 3.2 0.67/0.33 90 D47 20.2 3.1 0.64/.035 200 D48 20.9 3.1 0.32/0.64 425 D49 21.3 3.1 0.43/0.55 380 D50 20.7 3.3 0.37/0.61 360 D51 15.2 3.2 0.52/0.48 260 D52 19.0 3.3 0.36/0.62 350 D53 20.3 3.1 0.38/0.61 440 D54 19.0 3.3 0.34/0.63 350 D55 20.8 3.2 0.36/0.63 400 D56 18.6 3.1 0.34/0.62 330 D57 20.2 3.2 0.46/0.51 410 D58 19.6 3.3 0.20/0.52 315 D59 21.0 3.2 0.36/0.61 330 D60 20.7 3.3 0.32/0.61 310 D61 20.3 3.5 0.22/0.56 280 D62 20.6 3.4 0.24/0.57 360 D63 21.3 3.2 0.32/0.63 360 D64 23.3 3.5 0.23/0.54 180 D65 21.0 3.5 0.28/0.59 310 D66 20.8 3.1 0.40/0.59 470 D67 20.5 3.3 0.37/0.62 390 D68 21.8 3.2 0.35/0.62 400 D69 20.2 3.3 0.36/0.61 270 D70 19.8 3.3 0.42/0.55 430 D71 18.8 3.2 0.47/0.51 410 D72 18.3 3.3 0.46/0.50 200 D73 19.1 3.3 0.35/0.53 110 D74 19.5 3.3 0.42/0.54 410 D75 21.4 3.2 0.31/0.63 390 D76 19.6 3.3 0.43/0.55 380 D77 21.1 3.3 0.33/0.63 400 D78 20.8 3.4 0.34/0.63 360 D79 22.1 3.3 0.47/0.51 420 D80 21.0 3.3 0.34/0.63 400 D81 20.5 3.4 0.39/0.58 190 D82 19.7 3.5 0.33/0.64 230 D83 20.4 3.4 0.33/0.63 290 D84 21.3 3.4 0.36/0.62 300 Ref-D9 18.1 3.1 0.34/0.62 70 Ref-D10 17.1 3.0 0.34/0.62 185 Ref-D11 17.1 3.2 0.31/0.63 95 Ref-D12 17.9 3.0 0.32/0.63 265 Ref-D13 18.4 3.2 0.33/0.63 150 Ref-D14 17.0 3.1 0.34/0.62 200

[0560] 3) Further Vacuum-Processed Blue-Emitting Components

[0561] In Examples D85 to D90 which follow (see Tables 7 and 8), the data of blue-emitting OLEDs are presented. Processing and characterization are as described in 2).

[0562] The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The parameter U1000 in table 8 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2. The lifetime LT50 is defined as the time after which the luminance drops to 50% of the starting luminance with a starting brightness of 1000 cd/m.sup.2.

TABLE-US-00078 TABLE 7 Construction of the blue vacuum-processed OLEDs HTL2 EBL EML HBL ETL Ex. thickness thickness thickness thickness thickness D85 HTM EBM1 M8:Ir(L64) ETM1 ETM1:ETM2 30 nm 10 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D86 HTM EBM1 M8:Ir(L64) ETM2 M300 30 nm 10 nm (85%:15%) 10 nm 30 nm 30 nm D87 HTM EBM1 M8:Ir(L64) ETM3 M200 30 nm 10 nm (85%:15%) 10 nm 30 nm 30 nm D88 HTM Ir(L100) M8:Ir(L64) ETM3 ETM1:ETM2 30 nm 10 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D89 HTM EBM1 M9:Ir(L107) ETM3 ETM1:ETM2 30 nm 10 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D90 HTM EBM1 M8:Ir(L114) ETM3 ETM1:ETM2 30 nm 10 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm

TABLE-US-00079 TABLE 8 Data of the blue vacuum-processed OLEDs Ex. EQE1000 (%) U1000 (V) CIE x/y LT50 (h) D85 17.1 4.3 0.17/0.38 1800 D86 18.6 4.5 0.18/0.38 2200 D87 16.3 4.7 0.18/0.39 2000 D88 18.8 4.5 0.18/0.38 2500 D89 5.1 5.7 0.16/0.11 D90 22.7 4.9 0.16/0.37 3400

[0563] 4) White-Emitting OLEDs

[0564] According to the general methods from 1), a white-emitting OLED having the following layer structure is produced:

TABLE-US-00080 TABLE 9 Structure of the white OLEDs EML EML EML HTL2 red blue green HBL ETL Ex. thickness thickness thickness thickness thickness thickness D-W1 HTM EBM1:Ir(L105) M8:M3:Ir(L64) M3:Ir116 ETM1 ETM1:ETM2 230 nm (97%:3%) (45%:50%:5%) (90%:10%) 10 nm (50%:50%) 9 nm 8 nm 7 nm 30 nm

TABLE-US-00081 TABLE 10 Device results Voltage (V) CIE x/y LD50 EQE (%) 1000 1000 cd/m.sup.2 (h) Ex. 1000 cd/m.sup.2 cd/m.sup.2 CRI 1000 cd/m.sup.2 D-W1 21.8 6.1 0.43/0.46 7500 83

[0565] Solution-Processed Devices:

[0566] A: From Soluble Functional Materials of Low Molecular Weight

[0567] The iridium complexes of the invention may also be processed from solution and lead therein to OLEDs which are much simpler in terms of process technology compared to the vacuum-processed OLEDs, but nevertheless have good properties. The production of such components is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (for example in WO 2004/037887). The structure is composed of substrate/ITO/hole injection layer (60 nm)/interlayer (20 nm)/emission layer (60 nm)/hole blocker layer (10 nm)/electron transport layer (40 nm)/cathode. For this purpose, substrates from Technoprint (soda-lime glass) are used, to which the ITO structure (indium tin oxide, a transparent conductive anode) is applied. The substrates are cleaned in a clean room with DI water and a detergent (Deconex 15 PF) and then activated by a UV/ozone plasma treatment. Thereafter, likewise in a clean room, a 20 nm hole injection layer is applied by spin-coating. The required spin rate depends on the degree of dilution and the specific spin-coater geometry. In order to remove residual water from the layer, the substrates are baked on a hotplate at 200 C. for 30 minutes. The interlayer used serves for hole transport; in this case, HL-X092 from Merck is used. The interlayer may alternatively also be replaced by one or more layers which merely have to fulfill the condition of not being leached off again by the subsequent processing step of EML deposition from solution. For production of the emission layer, the triplet emitters of the invention are dissolved together with the matrix materials in toluene or chlorobenzene. The typical solids content of such solutions is between 16 and 25 g/I when, as here, the layer thickness of 60 nm which is typical of a device is to be achieved by means of spin-coating. The solution-processed devices of type 1a contain an emission layer composed of M4:M5:IrL (40%:45%:15%), those of type 1b contain an emission layer composed of M4:M5:IrL (20%:60%:20%), and those of type 2 contain an emission layer composed of M4:M5:IrLa:IrLb (30%:34%:30%:6%); in other words, they contain two different Ir complexes. The emission layer is spun on in an inert gas atmosphere, argon in the present case, and baked at 160 C. for 10 min. Vapour-deposited above the latter are the hole blocker layer (10 nm ETM1) and the electron transport layer (40 nm ETM1 (50%)/ETM2 (50%)) (vapour deposition systems from Lesker or the like, typical vapour deposition pressure 510.sup.6 mbar). Finally, a cathode of aluminium (100 nm) (high-purity metal from Aldrich) is applied by vapour deposition. In order to protect the device from air and air humidity, the device is finally encapsulated and then characterized. The OLED examples cited are yet to be optimized; Table 11 summarizes the data obtained.

TABLE-US-00082 TABLE 11 Results with materials processed from solution EQE (%) Voltage LT50 (h) Emitter 1000 (V) 1000 Ex. Device cd/m.sup.2 1000 cd/m.sup.2 CIE x/y cd/m.sup.2 Green, yellow, orange and red OLEDs Sol-Ref- Ir5 15.0 6.2 0.68/0.32 4000 Red1 Type 1a Sol- Ir(L34) 15.7 6.5 0.57/0.43 40000 RedD1 Type 1a Sol-RedD2 Ir1 15.7 6.6 0.56/0.44 140000 Ir(L34) Type 2 Sol-RedD3 Ir109 16.1 6.5 0.56/0.44 200000 Ir(L34) Type 2 Sol-RedD4 Ir109 17.1 6.3 0.67/0.33 270000 Ir5 Type 2 Sol-RedD5 Ir1 17.4 6.1 0.64/0.36 210000 Ir(L1000) Type 2 Sol-RedD6 Ir1 17.0 6.1 0.62/0.37 545000 Ir(L1001) Type 2 Sol-RedD7 Ir1 17.8 6.3 0.64/0.36 210000 Ir1000 Type 2 Sol- Ir1 18.6 5.7 0.63/0.37 285000 RedD8 Ir1001 Type 2 Sol-RedD9 Ir1 18.5 6.2 0.63/0.37 77000 Ir1002 Type 2 Sol-RedD10 Ir1 19.3 5.4 0.62/0.38 282000 Ir1003 Type 2 Sol-RedD11 Ir1 17.6 5.9 0.67/0.33 165000 Ir1005 Type 2 Sol-RedD12 Ir1 15.9 6.4 0.67/0.33 130000 Ir(L1200) Type 2 Sol Ir(L1) 16.1 6.5 0.67/0.33 120000 RedD13 Ir(L1200) Type 2 Sol Ir(L104) 18.1 4.8 0.66/0.34 70000 RedD14 Type 1b Sol Ir110 19.1 4.8 0.65/0.34 470000 RedD15 Ir(L104) Type 2 Sol-RedD16 Ir1 18.2 6.0 0.65/0.35 250000 Ir(L1009) Type 2 Sol-RedD17 Ir1 18.4 6.4 0.66/0.34 270000 Ir1007 Type 2 Sol-RedD18 Ir116 18.0 5.9 0.60/0.40 350000 Ir(L1036) Type 2 Sol-RedD19 Ir1 17.8 6.1 0.64/0.36 255000 Ir(L1021) Type 2 Sol-RedD20 Ir1 18.3 5.8 0.57/0.43 240000 Ir(L1008) Type 2 Sol-RedD21 Ir1 17.4 6.2 0.61/0.38 450000 Ir(L1019) Type 2 Sol-RedD22 Ir1 17.2 6.4 0.60/0.40 400000 Ir(L1017) Type 2 Sol Ir116 17.5 6.3 0.66/0.34 200000 RedD23 Ir(L1014) Type 2 Sol Ir1 17.5 6.3 0.66/0.34 200000 RedD24 Ir(L1014) Type 2 Sol Ir110 17.2 6.8 0.68/0.32 180000 RedD25 Ir(L1020) Type 2 Sol Ir1 17.0 6.0 0.63/0.36 140000 RedD26 Ir(L1024) Type 2 Sol Ir1 17.8 6.3 0.62/0.38 320000 RedD27 Ir1019 Type 2 Sol Ir1 17.6 6.1 0.65/0.35 300000 RedD28 Ir1017 Type 2 Sol Ir1 17.2 6.4 0.63/0.36 370000 RedD29 Ir1008 Type 2 Sol Ir110 18.0 6.0 0.64/0.36 330000 RedD30 Ir1040 Type 2 Sol-Ref- Ir1 19.8 5.2 0.36/0.61 200000 Green1 Type 1a Sol- Ir109 20.9 5.2 0.40/0.59 450000 GreenD1 Type 1a Sol-Ref- Ir1 19.6 4.8 0.36/0.61 220000 Green2 Type 1b Sol- Ir110 23.3 4.4 0.34/0.62 360000 GreenD2 Type 1b Sol- Ir114 21.1 4.4 0.36/0.62 55000 GreenD3 Type 1b Sol- Ir116 21.6 4.5 0.34/0.63 240000 GreenD4 Type 1b Sol- Ir118 21.1 4.8 0.34/0.62 160000 GreenD5 Type 1b Sol- Ir700 15.2 5.8 0.40/0.60 240000 GreenD6 Type 1b Sol- Ir702 16.3 5.7 0.39/0.61 280000 GreenD7 Type 1b Sol- Ir704 16.1 5.8 0.39/0.61 270000 GreenD8 Type 1b Sol- Ir705 15.9 5.7 0.40/0.60 300000 GreenD9 Type 1b Sol- Ir705-D3 16.1 5.8 0.40/0.59 320000 GreenD10 Type 1b Sol- Ir721 19.9 5.0 0.33/0.64 330000 GreenD11 Type 1b Sol- Ir722 20.6 5.2 0.33/0.64 300000 GreenD12 Type 1b Sol- Ir740 20.1 5.0 0.37/0.61 320000 GreenD13 Type 1b Sol- Ir101 21.1 4.5 0.38/0.60 350000 GreenD14 Type 1b Sol- Ir106 21.3 4.5 0.37/0.62 270000 GreenD15 Type 1b Sol- Ir107 19.9 4.3 0.39/0.60 400000 GreenD16 Type 1b Sol- Ir113 23.0 4.4 0.34/0.62 260000 GreenD17 Type 1b Sol- Ir111 22.2 4.6 0.35/0.63 360000 GreenD18 Type 1b Sol- Ir112 21.9 4.5 0.34/0.63 350000 GreenD19 Type 1b Sol- Ir115 21.1 4.2 0.33/0.61 390000 GreenD20 Type 1b Sol- Ir120 20.7 4.6 0.34/0.62 290000 GreenD21 Type 1b Sol- Ir122 20.0 4.2 0.36/0.61 310000 GreenD22 Type 1b Sol- Ir124 22.4 4.5 0.35/0.61 340000 GreenD23 Type 1b Sol- Ir126 21.7 4.2 0.35/0.62 400000 GreenD24 Type 1b Sol- Ir127 21.8 4.2 0.35/0.62 390000 GreenD25 Type 1b Sol- Ir128 21.5 4.3 0.35/0.63 420000 GreenD26 Type 1b Sol- Ir129 21.0 4.1 0.37/0.60 340000 GreenD27 Type 1b Sol- Ir131 23.0 4.4 0.35/0.62 310000 GreenD28 Type 1b Sol- Ir132 22.8 4.4 0.35/0.62 320000 GreenD29 Type 1b Sol- Ir133 19.0 4.5 0.42/0.57 310000 GreenD30 Type 1b Sol- Ir136 20.3 4.5 0.37/0.60 220000 GreenD31 Type 1b Sol- Ir138 21.5 4.3 0.37/0.61 280000 GreenD32 Type 1b Sol- Ir141 21.7 4.5 0.34/0.63 140000 GreenD33 Type 1b Sol- Ir143 22.7 4.4 0.38/0.61 340000 GreenD34 Type 1b Sol- Ir146 21.9 4.4 0.35/0.62 340000 GreenD35 Type 1b Sol- Ir151 22.4 4.5 0.41/0.58 430000 GreenD36 Type 1b Sol- Ir201 20.0 4.3 0.36/0.61 340000 GreenD37 Type 1b Sol- Ir203 21.7 4.4 0.34/0.63 380000 GreenD38 Type 1b Sol- Ir205 22.1 4.4 0.39/0.59 400000 GreenD39 Type 1b Sol- Ir308 20.8 4.5 0.35/0.62 350000 GreenD40 Type 1b Sol- Ir(L11) 21.1 4.6 0.43/0.56 300000 GreenD41 Type 1b Sol- Ir(L23) 21.6 4.4 0.34/0.61 190000 GreenD42 Type 1b Sol- Ir(L25) 17.2 5.8 0.39/0.60 260000 GreenD43 Type 1b Sol- Ir(L27) 19.9 4.8 0.45/0.52 360000 GreenD44 Type 1b Sol- Ir(L96) 20.3 4.6 0.35/0.62 390000 GreenD45 Type 1b Sol- Ir(L118) 23.1 4.5 0.34/0.62 200000 GreenD46 Type 1b Sol- IrL(146) 20.2 4.3 0.31/0.64 380000 GreenD47 Type 1b Sol- Ir(L208) 19.5 4.5 0.38/0.60 340000 GreenD48 Type 1b Sol- Ir(L130) 16.8 4.6 0.36/0.60 160000 GreenD49 Type 1b Sol- Ir(L47) 19.3 4.5 0.39/0.58 400000 GreenD50 Type 1b Sol- Ir(L53) 20.9 4.7 0.46/0.51 260000 GreenD51 Type 1b Sol- Ir(L218) 20.3 4.6 0.38/0.59 390000 GreenD52 Type 1b Sol- Ir(L226) 21.9 4.4 0.47/0.50 180000 GreenD53 Type 1b Sol- Ir(L273) 20.0 4.5 0.37/0.61 400000 GreenD54 Type 1b Sol- Ir(L280) 6.3 4.9 0.39/0.55 GreenD55 Type 1a Sol- Ir(L302) 22.4 4.4 0.35/0.63 350000 GreenD56 Type 1b Sol- Ir801 20.3 4.6 0.34/0.62 410000 GreenD57 Type 1b Sol- IrL802 21.0 4.5 0.39/0.59 380000 GreenD58 Type 1b

[0568] B: From Polymeric Functional Materials:

[0569] Production of the OLEDs as described in A. For production of the emission layer, the polymers of the invention are dissolved in toluene. The typical solids content of such solutions is between 10 and 15 g/I when, as here, the layer thickness of 40 nm which is typical of a device is to be achieved by means of spin-coating. The OLED examples cited are yet to be optimized; Table 12 summarizes the data obtained.

TABLE-US-00083 TABLE 12 Results with materials processed from solution EQE (%) Voltage (V) CIE x/y Ex. Polymer 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Green OLEDs D-P1 P1 19.8 4.1 0.39/0.59 Yellow OLEDs D-P2 P2 20.0 4.0 0.43/0.55 D-P3 P3 19.7 4.0 0.42/0.56

TABLE-US-00084 TABLE 13 Structural formulae of the materials used [01786] [01787] [01788] [01789] [01790] [01791] [01792] [01793] [01794] [01795] [01796] [01797] [01798] [01799] [01800] [01801] [01802] [01803] [01804] [01805] [01806] [01807] *: G. St-Pierre et al., Dalton Trans, 2011, 40, 11726.

DESCRIPTION OF THE FIGURES

[0570] FIG. 1: Single crystal structure of the compound KU) (ORTEP representation with 50% probability level)

[0571] a) View along the (pseudo) C.sub.3 axis

[0572] b) Lateral view of the (pseudo) C.sub.3 axis

[0573] The hydrogen atoms are not shown for better clarity.

[0574] FIG. 2: Single crystal structure of the compound Ir(L48) (ORTEP representation with 50% probability level)

[0575] a) View along the (pseudo) C.sub.3 axis

[0576] b) Lateral view of the (pseudo) C.sub.3 axis

[0577] The hydrogen atoms are not shown for better clarity.

[0578] FIG. 3: Single crystal structure of the compound Ir(L72) (ORTEP representation with 50% probability level)

[0579] a) View along the (pseudo) C.sub.3 axis

[0580] b) Lateral view of the (pseudo) C.sub.3 axis

[0581] The hydrogen atoms are not shown for better clarity.

[0582] FIG. 4: Single crystal structure of the compound Ir(L111) (ORTEP representation with 50% probability level)

[0583] a) View along the (pseudo) C.sub.3 axis

[0584] b) Lateral view of the (pseudo) C.sub.3 axis

[0585] The hydrogen atoms are not shown for better clarity.

[0586] FIG. 5: Single crystal structure of the compound Ir(L116) (ORTEP representation with 50% probability level)

[0587] a) View along the (pseudo) C.sub.3 axis

[0588] b) Lateral view of the (pseudo) C.sub.3 axis

[0589] The hydrogen atoms are not shown for better clarity.