Metal complexes

Abstract

The present invention relates to metal complexes of formula (1):
M(L).sub.n(L).sub.m(1) which comprises a moiety M(L).sub.n of formula (2): ##STR00001##
and to electronic devices, in particular organic electroluminescent devices, comprising these metal complexes.

Claims

1. A compound of formula (1):
M(L).sub.n(L).sub.m(1) which comprises a moiety M(L).sub.n of formula (2): ##STR00879## wherein M is iridium or platinum; CyC is an aryl or heteroaryl group having 5 to 18 aromatic ring atoms or a fluorene group, wherein CyC is coordinated to M via a carbon atom, is optionally substituted by one or more radicals R, and is bonded to CyD via a covalent bond wherein CyC and CyD are optionally linked to one another via a group selected from the group consisting of C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2, NR.sup.1, O, and S; CyD is a heteroaryl group having 5 to 18 aromatic ring atoms, wherein CyD is coordinated to M via a neutral nitrogen atom or via a carbene carbon atom, is optionally substituted by one or more radicals R, and is bonded to CyC via a covalent bond wherein CyD and CyC are optionally linked to one another via a group selected from the group consisting of C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2, NR.sup.1, O, and S; R is on each occurrence, identically or differently, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R, wherein one or more non-adjacent CH.sub.2 groups is 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 and wherein one or more H atoms is optionally replaced by D, F, Cl, Br, I, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group, or arylheteroaryl-amino group having 10 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1; and wherein two adjacent radicals R optionally form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; R.sup.1 is on each occurrence, identically or differently, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent CH.sub.2 groups is 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 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2; R.sup.2 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic, and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by F; and wherein two or more substituents R.sup.2 optionally form a mono- or polycyclic, aliphatic ring system with one another; L is, identically or differently on each occurrence, a co-ligand; n is 1, 2, or 3; m is 0, 1, 2, 3, or 4; and wherein a plurality of ligands L are optionally linked to one another or L is optionally linked to L via a single bond or a divalent or trivalent bridge and thus form a tridentate, tetradentate, pentadentate, or hexadentate ligand system; a substituent R optionally additionally coordinates to the metal; and wherein CyD and/or CyC contain(s) two adjacent carbon atoms which are each substituted by radicals R, wherein the respective radicals R, together with the C atoms, form a ring of formula (3) or (4): ##STR00880## wherein R.sup.1 and R.sup.2 are as defined above and the dashed bonds indicate the linking of the two carbon atoms in the ligand; A.sup.1 is C(R.sup.3).sub.2, or NR.sup.3; A.sup.2 is C(R.sup.1).sub.2, O, S, NR.sup.3, or C(O); A.sup.3 is C(R.sup.3).sub.2, NR.sup.3, or C(O); G is an alkylene group having 1, 2 or 3 C atoms and is optionally substituted by one or more radicals R.sup.2, CR.sup.2CR.sup.2, or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms optionally substituted by one or more radicals R.sup.2; and R.sup.3 is, identically or differently on each occurrence, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent CH.sub.2 groups is 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 and wherein one or more H atoms is optionally replaced by D or F, an aromatic or hetero aromatic ring system having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aryloxy or heteroaryloxy group having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, or an aralkyl or heteroaralkyl group having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.2; wherein two radicals R.sup.3 bonded to the same carbon atom optionally form an aliphatic or aromatic ring system with one another to form a spiro system; and wherein R.sup.3 optionally forms an aliphatic ring system with an adjacent radical R or R.sup.1; with the proviso that two heteroatoms are not bonded directly to one another in A.sup.1-A.sup.2-A.sup.3 and with the proviso that the radicals R on CyC do not join together to form a ring with the radicals R on CyD.

2. The compound of claim 1, wherein when M is iridium(III), n is 1, 2 or 3, and when M is platinum(II), n is 1 or 2.

3. The compound of claim 1, wherein CyC is selected from the group consisting of formulae (CyC-1) to (CyC-19), wherein CyC is in each case bonded to CyD at the position denoted by # and is coordinated to the metal at the position denoted by *: ##STR00881## ##STR00882## ##STR00883## wherein X is on each occurrence, identically or differently, CR or N; and W is on each occurrence, identically or differently, NR, O, S, or CR.sub.2.

4. The compound of claim 1, wherein CyC is selected from the group consisting of formulae (CyC-1a) to (CyC-19a), wherein CyC is in each case bonded to CyD at the position denoted by # and is coordinated to the metal at the position denoted by *: ##STR00884## ##STR00885## ##STR00886## ##STR00887## wherein W is on each occurrence, identically or differently, NR, O, S, or CR.sub.2.

5. The compound of claim 1, wherein CyD is selected from the group consisting of formulae (CyD-1) to (CyD-10), wherein CyD is in each case bonded to CyC at the position denoted by # and is coordinated to the metal at the position denoted by *: ##STR00888## ##STR00889## wherein X is on each occurrence, identically or differently, CR or N; and W is on each occurrence, identically or differently, NR, O, S, or CR.sub.2.

6. The compound of claim 1, wherein CyD is selected from the group consisting of formulae (CyD-1a) to (CyD-10a), wherein CyD is in each case bonded to CyC at the position denoted by # and is coordinated to the metal at the position denoted by *: ##STR00890## ##STR00891## wherein W is on each occurrence, identically or differently, NR, O, S, or CR.sub.2.

7. The compound of claim 1, wherein CyC comprises a group of formula (3) or (4) and is selected from the group consisting of formulae (CyC-1-1) to (CyC-19-1) and/or CyD comprises a group of formula (3) or (4) and is selected from the group consisting of formulae (CyD 1-1) to (CyD-10-1): ##STR00892## ##STR00893## ##STR00894## ##STR00895## ##STR00896## ##STR00897## wherein X is on each occurrence, identically or differently, CR or N; and W is on each occurrence, identically or differently, NR, O, S, or CR.sup.2; in each case denotes the positions which stand for CR, wherein the respective radicals R, together with the C atoms to which they are bonded, form a ring of formula (3) or (4), where the group of formulae (CyC-1-1) to (CyC-19-1) is in each case bonded to CyD at the position denoted by # and is coordinated to the metal at the position denoted by *, and where the groups of formula (CyD-1-1) to (CyD-10-1) is in each case bonded to CyC at the position denoted by # and is coordinated to the metal at the position denoted by *.

8. The compound of claim 1, wherein the compound is selected from the group consisting of formulae (17) to (22): ##STR00898## wherein V is a single bond or a bridging unit containing 1 to 80 atoms from the third, fourth, fifth, and/or sixth main group or a 3- to 6-membered homocycle or heterocycle which covalently bonds L to one another or L to L.

9. An oligomer, polymer, or dendrimer comprising one or more compounds of claim 1, wherein one or more bonds are present from the compound to the polymer, oligomer, or dendrimer.

10. A formulation comprising a compound of claim 1 and at least one further compound.

11. A formulation comprising an oligomer, polymer, or dendrimer of claim 9 and at least one further compound.

12. An electronic device comprising at least one compound of claim 1.

13. The electronic device of claim 12, where 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, and organic laser diodes.

14. An electronic device comprising at least one oligomer, polymer, or dendrimer of claim 9.

15. The electronic device of claim 14, 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, and organic laser diodes.

16. An organic electroluminescent device comprising a compound of claim 1 employed as an emitting compound in one or more emitting layers optionally in combination with a matrix material.

17. The compound of claim 1, wherein R is on each occurrence, identically or differently, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.1, wherein one or more non-adjacent CH.sub.2 groups is 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 and wherein one or more H atoms is optionally replaced by D, F, Cl, Br, I, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group, or arylheteroaryl-amino group having 10 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1.

18. The compound of claim 1, wherein the structure of formula (3) is selected from the group consisting of formulae (3-A), (3-B), (3-C), (3-D), and (3-E): ##STR00899## wherein A.sup.1 is C(R.sup.3).sub.2, or NR.sup.3; A.sup.2 is O or NR.sup.3; A.sup.3 is NR.sup.3; and R.sup.1 and R.sup.3 are defined as in claim 1, and the structure of formula (4) is selected from the group consisting of formulae (4-A), (4-B) and (4-C): ##STR00900##

19. An organic electroluminescent device comprising an oligomer, polymer, or dendrimer of claim 9 employed as an emitting compound in one or more emitting layers optionally in combination with a matrix material.

20. A compound of formula (1):
M(L).sub.n(L).sub.m(1) which comprises a moiety M(L).sub.n of formula (2): ##STR00901## wherein M is iridium or platinum; CyC is an aryl or heteroaryl group having 5 to 18 aromatic ring atoms or a fluorene group, wherein CyC is coordinated to M via a carbon atom, is optionally substituted by one or more radicals R, and is bonded to CyD via a covalent bond wherein CyC and CyD are optionally linked to one another via a group selected from the group consisting of C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2, NR.sup.1, O, and S; CyD is a heteroaryl group having 5 to 18 aromatic ring atoms, wherein CyD is coordinated to M via a neutral nitrogen atom or via a carbene carbon atom, is optionally substituted by one or more radicals R, and is bonded to CyC via a covalent bond wherein CyD and CyC are optionally linked to one another via a group selected from the group consisting of C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2, NR.sup.1, O, and S; R is on each occurrence, identically or differently, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.1, wherein one or more non-adjacent CH.sub.2 groups is 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 and wherein one or more H atoms is optionally replaced by D, F, Cl, Br, I, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group, or arylheteroaryl-amino group having 10 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1; and wherein two adjacent radicals R optionally form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; R.sup.1 is on each occurrence, identically or differently, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent CH.sub.2 groups is 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 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2; and wherein two or more adjacent radicals R.sup.1 with one another or R.sup.1 with R optionally form a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system; R.sup.2 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic, and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by F; and wherein two or more substituents R.sup.2 optionally form a mono- or polycyclic, aliphatic ring system with one another; L is, identically or differently on each occurrence, a co-ligand; n is 1, 2, or 3; m is 0, 1, 2, 3, or 4; and wherein a plurality of ligands L are optionally linked to one another or L is optionally linked to L via a single bond or a divalent or trivalent bridge and thus form a tridentate, tetradentate, pentadentate, or hexadentate ligand system; a substituent R optionally additionally coordinates to the metal; and wherein CyD contain(s) two adjacent carbon atoms which are each substituted by radicals R, wherein the respective radicals R, together with the C atoms, form a ring of formula (3) or (4): ##STR00902## wherein R.sup.1 and R.sup.2 are as defined above and the dashed bonds indicate the linking of the two carbon atoms in the ligand; A.sup.1 is C(R.sup.3).sub.2, S, or NR.sup.3; A.sup.2 is C(R.sup.1).sub.2, O, S, NR.sup.3, or C(O); A.sup.3 is C(R.sup.3).sub.2, O, S, NR.sup.3, or C(O); G is an alkylene group having 1, 2 or 3 C atoms and is optionally substituted by one or more radicals R.sup.2, CR.sup.2CR.sup.2, or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms optionally substituted by one or more radicals R.sup.2; and R.sup.3 is, identically or differently on each occurrence, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.2 wherein one or more non-adjacent CH.sub.2 groups is 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 and wherein one or more H atoms is optionally replaced by D or F, an aromatic or hetero aromatic ring system having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aryloxy or heteroaryloxy group having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, or an aralkyl or heteroaralkyl group having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.2; wherein two radicals R.sup.3 bonded to the same carbon atom optionally form an aliphatic or aromatic ring system with one another to form a spiro system; and wherein R.sup.3 optionally forms an aliphatic ring system with an adjacent radical R or R.sup.1; with the proviso that two heteroatoms are not bonded directly to one another in A.sup.1-A.sup.2-A.sup.3 and with the proviso that the radicals R on CyC do not join together to form a ring with the radicals R on CyD.

21. An organic electroluminescent device comprising a compound of claim 20.

22. A compound of formula (1):
M(L).sub.n(L).sub.m(1) which comprises a moiety M(L).sub.n of formula (2): ##STR00903## wherein M is iridium or platinum; CyC is an aryl or heteroaryl group having 5 to 18 aromatic ring atoms or a fluorene group, wherein CyC is coordinated to M via a carbon atom, is optionally substituted by one or more radicals R, and is bonded to CyD via a covalent bond wherein CyC and CyD are optionally linked to one another via a group selected from the group consisting of C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2, NR.sup.1, O, and S; CyD is a heteroaryl group having 5 to 18 aromatic ring atoms, wherein CyD is coordinated to M via a neutral nitrogen atom or via a carbene carbon atom, is optionally substituted by one or more radicals R, and is bonded to CyC via a covalent bond wherein CyD and CyC are optionally linked to one another via a group selected from the group consisting of C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2, NR.sup.1, O, and S; R is on each occurrence, identically or differently, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.1, wherein one or more non-adjacent CH.sub.2 groups is 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 and wherein one or more H atoms is optionally replaced by D, F, Cl, Br, I, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group, or arylheteroaryl-amino group having 10 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1; and wherein two adjacent radicals R optionally form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; R.sup.1 is on each occurrence, identically or differently, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent CH.sub.2 groups is 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 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2; and wherein two or more adjacent radicals R.sup.1 with one another or R.sup.1 with R optionally form a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system; R.sup.2 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic, and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by F; and wherein two or more substituents R.sup.2 optionally form a mono- or polycyclic, aliphatic ring system with one another; L.sup.1 is, identically or differently on each occurrence, a co-ligand; n is 2, or 3; m is 0, 1, 2, 3, or 4; and wherein a plurality of ligands L are optionally linked to one another or L is optionally linked to L via a single bond or a divalent or trivalent bridge and thus form a tridentate, tetradentate, pentadentate, or hexadentate ligand system; a substituent R optionally additionally coordinates to the metal; and wherein CyD and/or CyC contain(s) two adjacent carbon atoms which are each substituted by radicals R, wherein the respective radicals R, together with the C atoms, form a ring of formula (3) or (4): ##STR00904## wherein R.sup.1 and R.sup.2 are as defined above and the dashed bonds indicate the linking of the two carbon atoms in the ligand; A.sup.1 is C(R.sup.3).sub.2, or NR.sup.3; A.sup.2 is C(R.sup.1).sub.2, O, S, NR.sup.3, or C(O); A.sup.3 is C(R.sup.3).sub.2, NR.sup.3, or C(O); G is an alkylene group having 1, 2 or 3 C atoms and is optionally substituted by one or more radicals R.sup.2, CR.sup.2CR.sup.2, or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms optionally substituted by one or more radicals R.sup.2; and R.sup.3 is, identically or differently on each occurrence, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent CH.sub.2 groups is 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 and wherein one or more H atoms is optionally replaced by D or F, an aromatic or hetero aromatic ring system having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aryloxy or heteroaryloxy group having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, or an aralkyl or heteroaralkyl group having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.2; wherein two radicals R.sup.3 bonded to the same carbon atom optionally form an aliphatic or aromatic ring system with one another to form a spiro system; and wherein R.sup.3 optionally forms an aliphatic ring system with an adjacent radical R or R.sup.1; with the proviso that two heteroatoms are not bonded directly to one another in A.sup.1-A.sup.2-A.sup.3 and with the proviso that the radicals R on CyC do not join together to form a ring with the radicals R on CyD.

23. An organic electroluminescent device comprising a compound of claim 22.

Description

DESCRIPTION OF THE FIGURES

(1) The FIGURE shows the photoluminescence spectrum of a tris(phenylisoquinoline)iridium complex which contains a group of the formula (3), compared with the spectrum of the corresponding complex without the group of the formula (3). The spectra were measured in an approx. 10.sup.5 molar solution in degassed toluene at room temperature. The narrower emission band having a full width at half maximum (FWHM) value of 48 nm compared with 74 nm in the case of the compound without a group of the formula (3) is clearly evident.

EXAMPLES

(2) The following syntheses are carried out, unless indicated otherwise, in dried solvents under a protective-gas atmosphere. 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 numbers in square brackets or the numbers indicated for individual compounds relate to the CAS numbers of the compounds known from the literature.

A: Synthesis of the Synthones S

Example S1

1,1,2,2,3,3-Hexamethylindane-d18, S1

(3) ##STR00047##

(4) Preparation analogous to J. Baran, et al., J. Org. Chem. 1988, 53, 19, 4626.

(5) 18.7 ml (170 mmol) of titanium tetrachloride are added dropwise with vigorous stirring to a mixture, cooled to 78 C., of 160.7 g (1 mol) of 2-chloro-2-phenylpropane-d6 [53102-26-4], 230.8 g (2.4 mol) of 2,3-dimethylbut-2-ene-d12 [69165-86-2] and 2500 ml of anhydrous dichloromethane, and the mixture is stirred for a further 2 h. The cold reaction mixture is poured into 1500 ml of 3 N hydrochloric acid with vigorous stirring, stirred for a further 20 min., the organic phase is separated off, washed twice with 1000 ml of water each time, once with 500 ml of sat. sodium carbonate solution, once with 500 ml of saturated sodium chloride solution, dried over magnesium sulfate, the desiccant is filtered off, the filtrate is freed from dichloromethane in vacuo, and the residue is subjected to fractional distillation (core fraction 60-65 C., about 0.5 mbar). Yield: 163.1 g (740 mmol), 74%; purity: about 95% according to NMR.

(6) The following compounds are prepared analogously:

(7) TABLE-US-00003 Ex. Starting materials Product Yield S2 68% S3 0 49%

Example S4

Pinacolyl 1,1,3,3-tetramethylindane-5-boronate, S4-B

(8) ##STR00052##

A) 5-Bromo-1,1,3,3-tetramethylindane [169695-24-3], S4-Br

(9) ##STR00053##

(10) 0.6 g of anhydrous iron(III) chloride and then, dropwise with exclusion of light, a mixture of 25.6 ml (500 mol) of bromine and 300 ml of dichloromethane are added to a solution, cooled to 0 C., of 87.2 g (500 mmol) of 1,1,3,3-tetramethylindane [4834-33-7] in 1000 ml of dichloromethane at such a rate that the temperature does not exceed +5 C. The reaction mixture is stirred at room temperature for a further 16 h, 300 ml of saturated sodium sulfite solution are then slowly added, the aqueous phase is separated off, the organic phase is washed three times with 1000 ml of water each time, dried over sodium sulfate, filtered through a short silica-gel column, and the solvent is then stripped off. Finally, the solid is recrystallised once from a little (about 100-150 ml) ethanol. Yield: 121.5 g (480 mmol), 96%; purity: about 95% according to .sup.1H-NMR.

B) Pinacolyl 1,1,3,3-tetramethylindane-5-boronate, S4-B

(11) A mixture of 25.3 g (100 mmol) of S4-Br, 25.4 g (120 mmol) of bis(pinacolato)diborane [73183-34-3], 29.5 g (300 mmol) of potassium acetate, anhydrous, 561 mg (2 mmol) of tricyclohexylphosphine and 249 mg (1 mmol) of palladium(II) acetate and 400 ml of dioxane is stirred at 80 C. for 16 h. After removal of the solvent in vacuo, the residue is taken up in 500 ml of dichloromethane, filtered through a Celite bed, the filtrate is evaporated in vacuo until crystallisation commences, and finally about 100 ml of methanol are also added dropwise in order to complete the crystallisation. Yield: 27.9 g (93 mmol), 93%; purity: about 95% according to .sup.1H-NMR. Boronic acid esters formed as oil can also be reacted further without purification.

(12) The following compounds are prepared analogously:

(13) TABLE-US-00004 Starting Product Yield Ex. materials Bromide Boronic acid ester 2 steps S5 80% S6 78% S7 0 60% S8 81% S9 43% S10 0 78% S11 80% S12 68% S13 0 77% S14 79% S15 70% S16 54% S17 0 81% S18 56% S19 94% 1 step S20 00 82% S21 01 02 03 79% S22 04 05 06 23% S23 07 08 09 77%

Example S24

5,5,7,7-Tetramethyl-6,7-dihydro-5H-[2]pyridine, S24

(14) ##STR00110##

(15) Procedure analogous to D. L. Boger et al., J. Org. Chem., 1981, 46, 10, 2180.

(16) A mixture of 14.0 g (100 mmol) of 2,2,4,4-tetramethylcyclopentanone [4694-11-5], 9.0 ml (110 mmol) of pyrrolidine [123-75-1], 951 mg (5 mmol) of p-toluenesulfonic acid monohydrate [6192-52-5] and 500 ml of toluene is heated on a water separator until the separation of water is complete (typically about 16 h). The toluene is then removed in vacuo, and the oily residue is subjected to a bulb-tube distillation. The 17.4 g (90 mmol) of 1-(3,3,5,5-tetramethylcyclopent-1-enyl)pyrrolidine obtained as amber-coloured oil are taken up in 50 ml of chloroform and slowly added dropwise at room temperature to a solution of 10.5 g (130 mmol) of 1,2,4-triazine in 50 ml of chloroform. When the addition is complete, the orange solution is stirred at room temperature for a further 2 h, and the temperature is then raised to 50 C., and the mixture is stirred for a further 45 h. After removal of the chloroform in vacuo, the residue is chromatographed on silica gel with diethyl ether:n-heptane (1:1, vv). Yield: 8.9 g (51 mmol), 51%; purity: about 97% according to .sup.1H-NMR.

(17) The following compounds are prepared analogously:

(18) TABLE-US-00005 Ex. Starting materials Product Yield S25 42% S26 37%

Example S27

5,6-Dibromo-1,1,2,2,3,3-hexamethylindane, S27

(19) ##STR00115##

(20) 1.3 g of anhydrous iron(III) chloride and then, dropwise with exclusion of light, a mixture of 64.0 ml (1.25 mol) of bromine and 300 ml of dichloromethane are added to a solution of 101.2 g (500 mmol) of 1,1,2,2,3,3-hexamethylindane [91324-94-6] in 2000 ml of dichloromethane at such a rate that the temperature does not exceed 25 C., if necessary counter-cooling using a cold-water bath. The reaction mixture is stirred at room temperature for a further 16 h, 500 ml of saturated sodium sulfite solution are then slowly added, the aqueous phase is separated off, the organic phase is washed three times with 1000 ml of water each time, dried over sodium sulfate, filtered through a short silica-gel column, and the solvent is then stripped off. Finally, the solid is recrystallised once from a little (about 100 ml) ethanol. Yield: 135.8 g (377 mmol), 75%; purity: about 95% according to .sup.1H-NMR.

(21) The following compounds are prepared analogously:

(22) TABLE-US-00006 Ex. Starting materials Product Yield S28 78% S29 73% S30 0 76% S31 80% S32 77% S33 19% S34 23%

Example S35

5,6-Diamino-1,1,2,2,3,3-hexamethylindane, S35

(23) ##STR00130##

A: 5,6-Dinitro-1,1,2,2,3,3-tetramethylindane, S35a

(24) ##STR00131##

(25) 350 ml of 100% by weight nitric acid are slowly added dropwise to a vigorously stirred mixture, cooled to 0 C., of 101.2 g (500 mmol) of 1,1,2,2,3,3-hexamethylindane [91324-94-6] and 350 ml of 95% by weight sulfuric acid at such a rate that the temperature does not exceed +5 C. The reaction mixture is subsequently allowed to warm slowly to room temperature over 2-3 h and is then poured into a vigorously stirred mixture of 6 kg of ice and 2 kg of water. The pH is adjusted to 8-9 by addition of 40% by weight NaOH, the mixture is extracted three times with 1000 ml of ethyl acetate each time, the combined org. phases are washed twice with 1000 ml of water each time, dried over magnesium sulfate, the ethyl acetate is then removed virtually completely in vacuo until crystallisation commences, and the crystallisation is completed by addition of 500 ml of heptane. The beige crystals obtained in this way are filtered off with suction and dried in vacuo. Yield: 136.2 g (466 mmol), 93%; purity: about 94% according to .sup.1H-NMR, remainder about 4% of 4,6-dinitro-1,1,3,3-tetramethylindane. About 3% of 4,5-dinitro-1,1,3,3-tetramethylindane, S35b, can be isolated from the mother liquor.

B: 5,6-Diamino-1,1,2,2,3,3-hexamethylindane, S35

(26) 136.2 g (466 mmol) of 5,6-dinitro-1,1,2,2,3,3-hexamethylindane, S35a, are hydrogenated at room temperature in 1200 ml of ethanol on 10 g of palladium/carbon at a hydrogen pressure of 3 bar for 24 h. The reaction mixture is filtered twice through a Celite bed, the brown solid obtained after removal of the ethanol is subjected to a bulb-tube distillation (T about 160 C., p about 10.sup.4 mbar). Yield: 98.5 g (424 mmol), 91%; purity: about 95% according to .sup.1H-NMR.

(27) The following compounds are prepared analogously:

(28) TABLE-US-00007 Ex. Starting materials Product Yield S35b 2% S36 80% S37 84% S38 76% S39 0 68% S40 63% S41 77% S42 16%

Example S43

N-[2-(1,1,2,2,3,3-Hexamethylindan-5-yl)ethyl]benzamide, S43

(29) ##STR00148##

A: 1,1,2,2,3,3-Hexamethylindane-5-carboxaldehyde, S43a

(30) ##STR00149##

(31) 200 ml (500 mmol) of n-BuLi, 2.5 M in n-hexane, are added dropwise to a vigorously stirred solution, cooled to 78 C., of 140.6 g (500 mmol) of 5-bromo-1,1,2,2,3,3-hexamethylindane, S5-Br, in 1000 ml of THF at such a rate that the temperature does not exceed 55 C. When the addition is complete, the mixture is stirred for a further 30 min., and a mixture of 42.3 ml (550 mmol) of DMF and 50 ml of THF is then allowed to run in with vigorous stirring. The mixture is stirred at 78 C. for a further 1 h, then allowed to warm to room temperature and quenched by addition of 300 ml of saturated ammonium chloride solution. The organic phase is separated off, the THF is removed in vacuo, the residue is taken up in 500 ml of ethyl acetate, washed once with 300 ml of 5% hydrochloric acid, twice with 300 ml of water each time, once with 300 ml of saturated sodium chloride solution, the organic phase is dried over magnesium sulfate, and the solvent is then removed in vacuo. The residue is employed in step B without further purification. Yield: 107.1 g (465 mmol), 93%; purity: about 95% according to .sup.1H-NMR.

(32) The following compounds can be prepared analogously:

(33) TABLE-US-00008 Ex. Starting material Product Yield S44a 0 91% S45a 89% S46a 95% S47a 90%

B: 2-(1,1,2,2,3,3-Hexamethyl-5-indanyl)ethylamine, S43b

(34) ##STR00158##

(35) A mixture of 80.6 g (350 mmol) of 1,1,2,2,3,3-Hexamethylindane-5-carboxaldehyde, S43a, 400 ml of nitromethane and 4.6 g (70 mmol) of ammonium acetate, anhydrous, is heated under reflux for 2 h until the starting material has been consumed (TLC check). After cooling, the reaction mixture is poured into 1000 ml of water, extracted three times with 300 ml of dichloromethane each time, the combined organic phases are washed three times with saturated sodium hydrogencarbonate solution, three times with 300 ml of water each time and once with 300 ml of saturated sodium chloride solution, dried over magnesium sulfate, and the solvent is removed in vacuo. The dark oily residue is dissolved in 100 ml of THF and slowly added dropwise with ice-cooling to a solution of 38.0 g (1.0 mol) of lithium aluminium hydride in 1000 ml of THF (care: exothermic reaction!). When the addition is complete, the reaction mixture is allowed to warm to room temperature and is stirred at room temperature for a further 20 h. The reaction mixture is hydrolysed with ice-cooling by slow addition of 500 ml of saturated sodium sulfate solution. The salts are filtered off with suction, rinsed with 500 ml of THF, the THF is removed in vacuo, the residue is taken up in 1000 ml of dichloromethane, the solution is washed three times with 300 ml of water each time, once with 300 ml of saturated sodium chloride solution, dried over magnesium sulfate, and the solvent is then removed in vacuo. The purification is carried out by bulb-tube distillation (p about 10.sup.4 mbar, T=200 C.). Yield: 67.0 g (273 mmol), 78%; purity: about 95% according to .sup.1H-NMR.

(36) The following compounds can be prepared analogously:

(37) TABLE-US-00009 Ex. Starting material Product Yield S44b 0 74% S45b 77% S46b 75% S47b 71%

C: N-[2-(1,1,2,2,3,3-Hexamethylindan-5-yl)ethyl]benzamide, S43

(38) A solution of 14.1 ml (100 mmol) of benzoyl chloride [98-88-4] in 100 ml of dichloromethane is added dropwise with vigorous stirring at 0 C. to a mixture of 24.5 g (100 mmol) of 2-(1,1,2,2,3,3-hexamethyl-5-indanyl)ethylamine, S43b, 14.1 ml (100 mmol) of triethylamine and 150 ml of dichloromethane at such a rate that the temperature does not exceed 30 C. The mixture is subsequently stirred at room temperature for a further 1 h. The dichloromethane is removed in vacuo, 100 ml of methanol are added to the colourless solid, which is filtered off with suction, washed three times with 50 ml of methanol and dried in vacuo. Yield: 31.1 g (89 mmol), 89%; purity: about 98% according to .sup.1H-NMR.

(39) The following compounds can be prepared analogously:

(40) TABLE-US-00010 Starting Carboxylic Ex. material acid chloride Product Yield S44 74% S45 0 77% S46 75% S47 71% S48 0 86% S49 88%

Example S50

2,7-Di-tert-butyl-9,9-(6-bromopyridin-2-yl)xanthene, S50

(41) ##STR00185##

(42) 120 ml (300 mmol) of n-BuLi, 2.5 M in n-hexane, are added at room temperature to a solution of 84.7 g (300 mmol) of di(4-tert-butylphenyl) ether [24085-65-2] in 1500 ml of diethyl ether, and the mixture is then stirred under reflux for 60 h. After the reaction mixture has been cooled to 10 C., 82.1 g (240 mmol) of bis(6-bromopyridin-2-yl)methanone are added in portions, and the mixture is then stirred at 10 C. for a further 1.5 h. The reaction mixture is quenched by addition of 30 ml of ethanol, the solvent is removed completely in vacuo in a rotary evaporator, the residue is taken up in 1000 ml of glacial acetic acid, 150 ml of acetic anhydride and then, dropwise, 30 ml of conc. sulfuric acid are added with stirring, and the mixture is stirred at 60 C. for a further 3 h. The solvent is then removed in vacuo, the residue is taken up in 1000 ml of dichloromethane, and the mixture is rendered alkaline by addition of 10% by weight aqueous NaOH with ice-cooling. The organic phase is separated off, washed three times with 500 ml of water each time, dried over magnesium sulfate, the organic phase is evaporated to dryness, and the residue is taken up in 500 ml of methanol, homogenised at elevated temperature and then stirred for a further 12 h, during which the product crystallises. The solid obtained after filtration with suction is dissolved in 1000 ml of dichloromethane, the solution is filtered through a Celite bed, the filtrate is evaporated to dryness, the residue is recrystallised twice from toluene:methanol (1:1) and then dried in vacuo. Yield: 56.3 g (87 mmol), 36%; purity: about 95% according to .sup.1H-NMR.

(43) The following compound can be prepared analogously:

(44) TABLE-US-00011 Ex. Starting material Product Yield S51 28%

Example S52

2,7-Di-tert-butyl-9,9-(6-bromopyridin-2-yl)xanthene, S52

(45) ##STR00188##

(46) Procedure analogous to G. Chen et al., Tetrahedron Letters 2007, 48, 3, 47. A vigorously stirred mixture of 56.2 g (200 mmol) of 5-bromo-1,1,2,2,3,3-hexamethylindane, S5-Br, 212.2 g (800 mmol) of tripotassium phosphate trihydrate, 300 g of glass beads (diameter 3 mm), 449 mg (2 mmol) of palladium(II) acetate, 809 mg (4 mmol) of tri-tert-butylphosphine and 1000 ml of dioxane is heated under reflux for 20 h. After cooling, the salts are filtered off with suction, rinsed with 300 ml of dioxane, the filtrate is evaporated in vacuo, the residue is taken up in 500 ml of ethyl acetate, the solution is washed three times with 300 ml of water each time, once with 300 ml of saturated sodium chloride solution, dried over magnesium sulfate, and the ethyl acetate is then removed in vacuo. The residue is purified by bulb-tube distillation (p about 10.sup.4 mbar, T about 180 C.). Yield: 32.6 g (78 mmol), 78%; purity: about 97% according to 1H-NMR.

Example S53

7-Bromo-1,2,3,4-tetrahydro-1,4-methanonaphthalene-6-carbaldehyde, S53

(47) ##STR00189##

(48) Procedure analogous to L. S. Chen et al., J. Organomet. Chem. 1980, 193, 283-292. 40 ml (100 mmol) of n-BuLi, 2.5 M in hexane, pre-cooled to 110 C., are added to a solution, cooled to 110 C., of 30.2 g (100 mmol) of 6,7-dibromo-1,2,3,4-tetrahydro-1,4-methanonaphthalene [42810-32-2] in a mixture of 1000 ml of THF and 1000 ml of diethyl ether at such a rate that the temperature does not exceed 105 C. The mixture is stirred for a further 30 min., a mixture, pre-cooled to 110 C., of 9.2 ml (120 mmol) of DMF and 100 ml of diethyl ether is then added dropwise, the mixture is then stirred for a further 2 h, allowed to warm to 10 C., 1000 ml of 2 N HCl are added, and the mixture is stirred at room temperature for a further 2 h. The organic phase is separated off, washed once with 500 ml of water, once with 500 ml of saturated sodium chloride solution, dried over magnesium sulfate, the solvent is removed in vacuo, and the residue is subjected to a bulb-tube distillation (T about 90 C., p about 10.sup.4 mbar). Yield: 15.8 g (63 mmol), 63%; purity: about 95% according to .sup.1H-NMR.

(49) The following compounds can be prepared analogously:

(50) TABLE-US-00012 Ex. Starting materials Product Yield S54 0 68% S55 66% S56 60% S57 54%

Example S58

7-(3,3-Dimethylbut-1-ynyl)-1,2,3,4-tetrahydro-1,4-methanonaphthalene-6-carbaldehyde, S58

(51) ##STR00198##

(52) 1.6 g (6 mmol) of triphenylphosphine, 674 mg (3 mmol) of palladium(II) acetate, 571 mg (30 mmol) of copper(I) iodide and 15.3 g (150 mmol) of phenylacetylene [536-74-3] are added consecutively to a solution of 25.1 g (100 mmol) of 7-bromo-1,2,3,4-tetrahydro-1,4-methanonaphthalene-6-carbaldehyde, S53, in a mixture of 200 ml of DMF and 100 ml of triethylamine, and the mixture is stirred at 65 C. for 4 h. After cooling, the precipitated triethylammonium hydrochloride is filtered off with suction, rinsed with 30 ml of DMF. The filtrate is freed from the solvents in vacuo. The oily residue is taken up in 300 ml of ethyl acetate, the solution is washed five times with 100 ml of water each time and once with 100 ml of saturated sodium chloride solution, and the organic phase is dried over magnesium sulfate. After removal of the ethyl acetate in vacuo, the oily residue is chromatographed on silica gel (n-heptane:ethyl acetate 99:1). Yield: 19.6 g (72 mmol), 72%; purity: about 97% according to .sup.1H-NMR.

(53) The following derivatives can be prepared analogously:

(54) TABLE-US-00013 Bromo- aryl- Ex. aldehyde Alkyne Product Yield S59 00 01 69% S60 02 03 04 69% S61 05 06 07 70% S62 08 09 0 66% S63 67% S64 70% S65 56%

B: Synthesis of the Ligands L

Example L1

2-(1,1,3,3-Tetramethylindan-5-yl)pyridine

(55) ##STR00220##

(56) 821 mg (2 mmol) of S-Phos and then 249 mg (1 mmol) of palladium(II) acetate are added to a mixture of 30.0 g (100 mmol) of pinacolyl 1,1,3,3-tetramethylindane-5-boronate, S4-B, 17.4 g (110 mmol) of 2-bromopyridine [109-04-6], 46.1 g (200 mmol) of tripotassium phosphate monohydrate, 300 ml of dioxane and 100 ml of water, and the mixture is heated under reflux for 16 h. After cooling, the aqueous phase is separated off, the organic phase is evaporated to dryness, the residue is taken up in 500 ml of ethyl acetate, the organic phase is washed three times with 200 ml of water each time, once with 200 ml of saturated sodium chloride solution, dried over magnesium sulfate, the desiccant is filtered off via a Celite bed, and the filtrate is re-evaporated to dryness. The oil obtained in this way is freed from low-boiling components and non-volatile secondary components by fractional bulb-tube distillation twice. Yield: 15.3 g (61 mmol), 61%; purity: about 99.5% according to .sup.1H-NMR.

(57) The following compounds are prepared analogously. Solids are freed from low-boiling components and non-volatile secondary components by recrystallisation and fractional sublimation (p about 10.sup.4-10.sup.5 mbar, T about 160-240 C.). Oils are purified by chromatography, subjected to fractional bulb-tube distillation or dried in vacuo in order to remove low-boiling components.

(58) TABLE-US-00014 Product Ex. Boronic acid ester Bromide Ligand Yield L2 66% L3 67% L4 64% L5 0 60% L6 61% L7 63% L8 0 63% L9 58% L10 60% L11 0 54% L12 59% L13 61% L14 48% L15 0 46% L16 66% L17 58% L18 0 59% L19 63% L20 65% L21 0 60% L22 64% L23 66% L24 68% L25 0 63% L26 45% L27 64% L28 00 01 65% L29 02 03 04 66% L30 05 06 07 67% L31 08 09 0 51% L32 64% L33 63% L34 61% L35 0 61% L36 62% L37 49% L38 0 57% L39 60% L40 59% L41 0 53%

Example 42

5,5,7,7-Tetramethyl-3-phenyl-6,7-dihydro-5H-[2]pyridine, L42

(59) ##STR00341##

(60) Procedure analogous to A. Mazzanti et al., Eur. J. Org. Chem., 2011, 6725.

(61) 40 ml (100 mmol) of n-butyllithium, 2.5 M in n-hexane, are added dropwise to a mixture, cooled to 78 C., of 10.5 ml (100 mmol) of bromobenzene and 500 ml of diethyl ether, and the mixture is stirred for a further 30 min. 17.5 g (100 mmol) of 5,5,7,7-tetramethyl-6,7-dihydro-5H-[2]pyridine, S24, are then added dropwise, the mixture is allowed to warm to room temperature, stirred for a further 12 h, quenched by addition of 100 ml of water, the organic phase is separated off, dried over magnesium sulfate. After removal of the solvent, the oily residue is chromatographed on silica gel with diethyl ether:n-heptane (3:7, v:v) and subsequently subjected to fractional bulb-tube distillation twice. Yield: 12.1 g (48 mmol), 48%; purity: about 99.5% according to .sup.1H-NMR.

(62) The following compounds can be prepared analogously. Solids are freed from low-boiling components and non-volatile secondary components by recrystallisation and fractional sublimation (p about 10.sup.4-10.sup.5 mbar, T about 160-240 C.). Oils are purified by chromatography, subjected to fractional bulb-tube distillation or dried in vacuo in order to remove low-boiling components.

(63) TABLE-US-00015 Ex. Pyridine Bromide Ligand Yield L43 50% L44 48% L45 0 46% L46 50% L47 47% L48 51% L49 0 49% L50 45% L51 46% L52 0 40%

Example 53

6,6,7,7,8,8-Hexamethyl-2-phenyl-7,8-dihydro-6H-cyclopenta[g]quinoxaline, L53

(64) ##STR00372##

(65) Procedure analogous to S. V. More et al., Tetrahedron Lett. 2005, 46, 6345.

(66) A mixture of 23.2 g (100 mmol) of 1,1,2,2,3,3-hexamethylindane-5,6-diamine, S35, 13.4 g (100 mmol) of oxophenylacetaldehyde [1074-12-0], 767 mg (3 mmol) of iodine and 75 ml of acetonitrile is stirred at room temperature for 16 h. The precipitated solid is filtered off with suction, washed once with 20 ml of acetonitrile, twice with 75 ml of n-heptane each time and then recrystallised twice from ethanol/ethyl acetate. Finally, the solid is freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.4-10.sup.5 mbar, T about 220 C.). Yield: 22.1 g (67 mmol), 67%; purity: about 99.5% according to .sup.1H-NMR.

(67) The following compounds are prepared analogously. Solids are freed from low-boiling components and non-volatile secondary components by recrystallisation and fractional sublimation (p about 10.sup.4-10.sup.5 mbar, T about 160-240 C.). Oils are purified by chromatography, subjected to fractional bulb-tube distillation or dried in vacuo in order to remove low-boiling components.

(68) TABLE-US-00016 Ex. Diamine Diketone Ligand Yield L54 58% L55 69% L56 0 60% L57 70% L58 48% L59 0 55% L60 68% L61 59% L62 62% L63 00 01 02 51%

Example 64

5,5,6,6,7,7-Hexamethyl-1,2-diphenyl-1,5,6,7-tetrahydroindeno [5,6-d]imidazol, L64

(69) ##STR00403##

(70) Procedure analogous to D. Zhao et al., Org. Lett., 2011, 13, 24, 6516. A mixture of 36.0 g (100 mmol) of 5,6-dibromo-1,1,2,2,3,3-hexamethylindane, 21.6 g (110 mmol) of N-phenylbenzamidine [1527-91-9], 97.8 g (300 mmol) of caesium carbonate, 100 g of molecular sieve 4A, 1.2 g (2 mmol) of xantphos, 449 mg (2 mmol) of palladium(II) acetate and 600 ml of o-xylene is heated under reflux with vigorous stirring for 24 h. After cooling, the salts are filtered off with suction via a Celite bed, rinsed with 500 ml of o-xylene, the solvent is removed in vacuo, and the residue is recrystallised three times from cyclohexane/ethyl acetate. Finally, the solid is freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.4-10.sup.5 mbar, T about 230 C.). Yield: 28.0 g (71 mmol), 71%; purity: about 99.5% according to .sup.1H-NMR.

(71) The following compounds are prepared analogously. Solids are freed from low-boiling components and non-volatile secondary components by recrystallisation and fractional sublimation (p about 10.sup.4-10.sup.5 mbar, T about 160-240 C.). Oils can be purified by chromatography, subjected to fractional bulb-tube distillation or dried in vacuo in order to remove low-boiling components.

(72) TABLE-US-00017 1,2-Dihalogen Ex. compound Benzamidine Ligand Yield L65 04 05 06 75% L66 07 08 09 77% L67 0 73% L68 68% L69 69% L70 0 71% L71 64% L72 36% L73 0 44% L74 43% L75 40% L76 38% L77 0 39%

Example 78

1,5,5,6,6,7,7-Heptamethyl-3-phenyl-1,5,6,7-tetrahydroindeno[5,6-d]imidazolium iodide, L78

(73) ##STR00443##

A) 5,5,6,6,7,7-Hexamethyl-1,5,6,7-tetrahydroindeno[5,6-d]imidazole

(74) ##STR00444##

(75) Procedure analogous to Z.-H. Zhang et al., J. Heterocycl. Chem. 2007, 44, 6, 1509. 1.3 g (5 mmol) of iodine are added to a vigorously stirred mixture of 116.2 g (500 mmol) of 1,1,2,2,3,3-hexamethylindane-5,6-diamine, S35, 90.9 ml (550 mmol) of triethoxymethane [122-51-0] and 400 ml of acetonitrile, and the mixture is stirred at room temperature for 5 h. The precipitated solid is filtered off with suction, washed once with a little acetonitrile, three times with 100 ml of n-heptane each time and dried in vacuo. Yield: 108.8 g (449 mmol), 90%; purity: about 97% according to .sup.1H-NMR.

B) 5,5,6,6,7,7-Hexamethyl-1-phenyl-1,5,6,7-tetrahydroindeno[5,6-d]-imidazole

(76) ##STR00445##

(77) Procedure analogous to S. Zhang et al., Chem. Commun. 2008, 46, 6170. A mixture of 24.2 g (100 mmol) of 5,5,6,6,7,7-hexamethyl-1,5,6,7-tetrahydroindeno[5,6-d]imidazole, A), 12.6 ml (120 mmol) of bromobenzene [108-86-1], 27.6 g (200 mmol) of potassium carbonate, 952 mg (5 mmol) of copper(I) iodide, 1.0 g (10 mmol) of N,N-dimethylglycine, 200 g of glass beads (diameter 3 mm) and 300 ml of DMSO is heated at 120 C. with vigorous stirring for 36 h. After cooling, the salts are filtered off with suction, rinsed with 1000 ml of ethyl acetate, the combined org. phases are washed five times with 500 ml of water each time, once with 500 ml of sat. sodium chloride solution, dried over magnesium sulfate, the solvent is removed in vacuo, and the residue is recrystallised twice from cyclohexane. Yield: 28.3 g (89 mmol), 89%; purity: about 97% according to .sup.1H-NMR.

C) 1,5,5,6,6,7,7-Heptamethyl-3-phenyl-1,5,6,7-tetrahydroindeno-[5,6-d]imidazolium iodide, L78

(78) 12.6 ml (200 mmol) of methyl iodide [74-88-4] are added with stirring to a suspension of 28.3 g (89 mmol) of 5,5,6,6,7,7-hexamethyl-1-phenyl-1,5,6,7-tetrahydroindeno[5,6-d]imidazole, B), in 100 ml of THF, and the mixture is stirred at 45 C. for 24 h. After cooling, the precipitated solid is filtered off with suction, washed three times with 50 ml of ethanol each time and dried in vacuo. Yield: 23.5 g (51 mmol), 57%; purity: about 99% according to .sup.1H-NMR.

(79) The following compounds are prepared analogously:

(80) TABLE-US-00018 Brominated aromatic compound Yield Ex. 1,2-Diamine Alkyl halide Ligand 3 steps L79 46% L80 0 43% L81 34% L82 41% L83 0 19% L84 37% L85 34% L86 43% L87 0 45% L88 40%

Example 89

1,4,4,6,6-Pentamethyl-3-phenyl-1,4,5,6-tetrahydrocyclopentaimidazolium iodide, L89

(81) ##STR00476##

A) 4,4,6,6-Tetramethyl-1,4,5,6-tetrahydrocyclopentaimidazole

(82) ##STR00477##

(83) Preparation analogous to G. Bratulescu, Synthesis, 2009, 14, 2319. An intimate mixture of 1.54 g (10.0 mmol) of 3,3,5,5-tetramethylcyclopentane-1,2-dione [20633-06-1], 4.21 g (3.0 mmol) of urotropin, 7.7 g (10 mmol) of ammonium acetate and 0.3 ml of glacial acetic acid is heated in a temperature-controlled microwave until an internal temperature of about 120 C. has been reached, and is then held at this temperature for about 15 min.

(84) After cooling, the mass is added to 150 ml of water, the pH is adjusted to 8 using aqueous ammonia solution (10% by weight) with stirring, the precipitated solid is then filtered off with suction and washed with water. After drying, the product is recrystallised from ethanol/ethyl acetate. Yield: 1.17 g (7.1 mmol), 71%; purity: about 98% according to .sup.1H-NMR.

B) 4,4,6,6-Tetramethyl-1-phenyl-1,4,5,6-tetrahydrocyclopentaimidazole

(85) ##STR00478##

(86) Preparation analogous to Example 78, B). Use of 1.64 g (10.0 mmol) of 4,4,6,6-tetramethyl-1,4,5,6-tetrahydrocyclopentaimidazole, A), the remaining starting materials and solvents are correspondingly adapted stoichiometrically. Yield: 1.53 g (6.3 mmol), 63%; purity: about 98% according to .sup.1H-NMR.

C) 1,4,4,6,6-Pentamethyl-3-phenyl-1,4,5,6-tetrahydrocyclopentaimidazolium iodide, L89

(87) Preparation analogous to Example 78, C). Use of 2.4 g (10.0 mmol) of 4,4,6,6-tetramethyl-1-phenyl-1,4,5,6-tetrahydrocyclopentaimidazole, B), the remaining starting materials and solvents are correspondingly adapted stoichiometrically. Yield: 2.26 g (5.9 mmol), 59%; purity: about 99% according to .sup.1H-NMR.

(88) The following compounds are prepared analogously:

(89) TABLE-US-00019 Brominated aromatic compound Yield Ex. 1,2-Dione Alkyl halide Ligand 3 steps L90 0 36% L91 40% L92 33%

Example 93

Ligands of the benzo[4,5]imidazo[2,1-c]quinazoline type

General Ligand Synthesis

From 2-amidoarylaldehydes and 1,2-diaminobenzenes

(90) ##STR00488##
Step A:

(91) A solution of 100 mmol of the 2-amidoarylaldehyde and 110 mmol of the 1,2-diaminobenzene in 70 ml of ethanol is placed in a 500 ml round-bottomed flask with water separator and stirred at 50 C. for 30 min. 70 ml of nitrobenzene are then added, and the temperature is increased stepwise to gentle reflux of the nitrobenzene, with the ethanol and water formed being distilled off during the heating. After 4 h under gentle reflux, the mixture is allowed to cool to 50 C., 40 ml of methanol are added, the mixture is then allowed to cool fully with stirring, stirred at room temperature for a further 2 h, the crystals of 2-(2-amidophenyl)benzimidazole formed are then filtered off with suction, washed twice with 20 ml of methanol each time and dried in vacuo. If the 2-(2-amidophenyl)benzimidazole does not crystallise out, the solvent is removed in vacuo, and the residue is employed in step B.

(92) Step B:

(93) Variant A:

(94) 350 mmol of the corresponding carbonyl chloride and 50 mmol of the corresponding carboxylic acid are added to a vigorously stirred mixture (precision glass stirrer) of 100 mmol of the 2-(2-amidophenyl)benzimidazole and 150 ml of dioxane or diethylene glycol dimethyl ether, and the mixture is heated under reflux (typically 4-48 h) until the 2-(2-amidophenyl)benzimidazole has reacted. Corresponding carbonyl chlorides and carboxylic acids are those which form the respective amide radical. After cooling, the reaction mixture is introduced with vigorous stirring into a mixture of 1000 g of ice and 300 ml of aqueous conc. ammonia. If the product is produced in the form of a solid, this is filtered off with suction, washed with water and sucked dry. If the product is produced in the form of an oil, this is extracted with three portions of 300 ml each of ethyl acetate or dichloromethane. The organic phase is separated off, washed with 500 ml of water and evaporated in vacuo. The crude product is taken up in ethyl acetate or dichloromethane, filtered through a short column of aluminium oxide, basic, activity grade 1, or silica gel in order to remove brown impurities. After recrystallisation (methanol, ethanol, acetone, dioxane, DMF, etc.) of the benzo[4,5]-imidazo[2,1-c]quinazoline obtained in this way, the latter is freed from low-boiling components and non-volatile secondary components by bulb-tube distillation or fractional sublimation (p about 10.sup.4-10.sup.5 mbar, T about 160-240 C.). Compounds containing aliphatic radicals having more than 6 C atoms, or those containing aralkyl groups having more than 9 C atoms, are typically purified by chromatography and then dried in vacuo in order to remove low-boiling components. Purity according to .sup.1H-NMR typically >99.5%.

(95) Variant B:

(96) Analogous procedure to variant A, but 50 mmol of water are added instead of the carboxylic acid.

(97) Variant C:

(98) Analogous procedure to variant A, but no carboxylic acid is added.

Example L93

(99) ##STR00489##
Step A:

(100) Use of 20.5 g (100 mmol) of S69 and 22.5 g (110 mmol) of S16.

(101) The 2,2-dimethyl-N-[2-(5,5,7,7-tetramethyl-1,5,6,6-tetrahydroindeno[5,6-d]-imidazol-2-yl)phenyl]propionamide crystallises out, yield 31.6 g (81 mmol) 81%; purity: 97% according to 1H-NMR.

(102) Step B, variant A:

(103) Use of 31.6 g (81 mmol) of 2,2-dimethyl-N-[2-(5,5,7,7-tetramethyl-1,5,6,6-tetrahydroindeno[5,6-d]imidazol-2-yl)phenyl]propionamide (step A), 120 ml of dioxane, 33.8 g (280 mmol) of pivaloyl chloride [3282-30-2] and 4.1 g (40 mmol) of pivalic acid [75-98-9], reaction time 16 h, the crude product is produced in the form of a solid on neutralisation, recrystallisation from DMF/ethanol, fractional sublimation of the product twice at T about 170 C., p about 10.sup.4 mbar. Yield: 19.3 g (52 mmol), 64%; purity: about 99.5% according to .sup.1H-NMR.

(104) The following compound is prepared analogously:

(105) TABLE-US-00020 2-Amidoaryl- 1,2-Diamino- Yield Ex. aldehyde benzene Ligand 2 steps L94 0 55%

Example L95

1,1,2,2,3,3-Hexamethyl-5-phenyl-2,3-dihydro-1H-6-aza-cyclopenta[b]naphthalene, L95

(106) ##STR00493##

(107) 17.0 g (120 mmol) of phosphorus pentoxide are added in portions with vigorous stirring at 90 C. to a solution of 34.8 g (100 mmol) of N-[2-(1,1,2,2,3,3-hexamethylindan-5-yl)ethyl]benzamide, S43, in 150 ml of o-xylene. 28.0 ml (300 mmol) of phosphoryl chloride are added dropwise to this reaction mixture, which is then stirred under reflux for a further 4 h. The reaction mixture cooled to 80 C. is poured onto 1000 g of ice with vigorous stirring and then rendered alkaline (pH about 12) by addition of solid NaOH. The mixture is extracted three times with 300 ml of toluene each time, the organic phase is washed three times with water, dried over magnesium sulfate, and the solvent is removed in vacuo. The oily residue is dissolved in 200 ml of o-dichlorobenzene, 86.9 g (1 mol) of manganese dioxide are added to the solution, and the mixture is subsequently boiled under reflux on a water separator for 16 h. After cooling, the manganese dioxide is filtered off via a Celite bed, the solid is washed with 500 ml of a mixture of dichloromethane and ethanol (10:1), and the combined filtrates are freed from the solvents in vacuo. The residue is recrystallised from cyclohexane/ethyl acetate and finally freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.4-10.sup.5 mbar, T about 230 C.). Yield: 20.1 g (61 mmol), 61%; purity: about 99.5% according to .sup.1H-NMR.

(108) The following compounds can be prepared analogously:

(109) TABLE-US-00021 Ex. Starting material Product Yield L96 66% L97 64% L98 60% L99 00 01 41% L100 02 03 67% L101 04 05 65%

Example L102

7,8,9,10-Tetrahydro-7,10-methano-6-phenylphenanthridine, L102

(110) ##STR00506##

(111) 14.2 g (100 mmol) of boron trifluoride etherate are added dropwise to a vigorously stirred mixture of 46.6 g (500 mmol) of aniline, 58.4 g (550 mmol) of benzaldehyde, 94.2 g (1 mol) of norbornene and 1300 ml of dichloromethane, and the mixture is then heated under reflux for 40 h. After cooling, the reaction mixture is washed twice with 400 ml of water each time, the organic phase is dried over magnesium sulfate, and the dichloromethane is then removed in vacuo. The residue is taken up in 1000 ml of o-dichlorobenzene, 435 g (5 mol) of manganese dioxide are added, and the mixture is heated under reflux on a water separator for 16 h. After cooling, 1000 ml of ethyl acetate are added, the manganese dioxide is filtered off with suction via a Celite bed, the manganese dioxide is rinsed with 1000 ml of ethyl acetate, and the combined filtrates are freed from the solvents in vacuo. The residue is recrystallised twice from cyclohexane and finally freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.4-10.sup.5 mbar, T about 230 C.). Yield: 76.0 g (280 mmol), 56%; purity: about 99.5% according to .sup.1H-NMR.

(112) The following compounds can be prepared analogously:

(113) TABLE-US-00022 Ex. Starting material Product Yield L103 07 08 66% L104 09 0 64% L105 56% L106 58% L107 61% L108 63% L109 0 58% L110 55% L111 60% L112 34% L113 69% L114 0 67% L115 23% 17% L116 50% L117 48% L118 68% L119 0 45% L120 65% L121 54% L122 38% L123 34% L124 0 36% L125 28% L126 32% L127 25%

Example L128

5,8-Methano-5,6,7,8-tetrahydro-3-phenyl-2-aza-anthracene, L128

(114) ##STR00558##

(115) A mixture of 13.6 g (50 mmol) of 7-(3,3-dimethylbut-1-ynyl)-1,2,3,4-tetrahydro-1,4-methanonaphthalene-6-carbaldehyde, S58, and 500 ml of methanolic ammonia solution (2 M) is stirred at 140 C. for 5 h in an autoclave. After cooling, the methanol is removed in vacuo, the oily residue is chromatographed on silica gel (n-heptane:ethyl acetate 95:5) and finally freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.4-10.sup.5 mbar, T about 230 C.). Yield: 5.1 g (17 mmol), 34%; purity: about 99.5% according to .sup.1H-NMR.

(116) The following derivatives can be prepared analogously:

(117) TABLE-US-00023 Ex. Starting material Product Yield L129 0 37% L130 29% L131 30% L132 32% L133 27% L134 0 30% L135 36%

Example L136

1R,4S-Methano-1,2,3,4-tetrahydro-9-phenyl-10-aza-phenanthrene, L136

(118) ##STR00573##

(119) One drop of conc. sulfuric acid is added to a mixture of 26.1 g (100 mmol) of 2-bromophenylphenylmethanone [13047-06-8], 11.1 g (100 mmol) of (1R,2R,4S)-bicyclo[2.2.1]heptan-2-amine [7242-92-4] and 23.3 ml (105 mmol) of tetraethoxysilane [78-10-4], and the mixture is then heated at 160 C. in a water separator for 16 h, during which the ethanol distils off. After cooling, 500 ml of diethyl ether are added to the residue, the mixture is washed twice with 100 ml of saturated sodium hydrogencarbonate solution each time and twice with 300 ml of water each time and then dried over magnesium sulfate. After removal of the diethyl ether, 27.6 g (200 mmol) of potassium carbonate, 5 g of palladium/carbon (5% by weight), 2.6 g (10 mmol) of triphenylphosphine, 100 g of glass beads (diameter 3 mm) and 300 ml of mesitylene are added to the oily residue, and the mixture is again heated under reflux for 16 h. After cooling, the salts are filtered off with suction via a Celite bed, rinsed with 500 ml of toluene, and the combined filtrates are evaporated to dryness in vacuo. The residue is recrystallised three times from DMF/ethanol and finally freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.4-10.sup.5 mbar, T about 230 C.). Yield: 14.9 g (55 mmol), 55%; purity: about 99.5% according to .sup.1H-NMR.

(120) The following derivatives can be prepared analogously:

(121) TABLE-US-00024 Ex. Starting material Product Yield L137 47% L138 45%

Example L139

Tetradentate Ligands

(122) ##STR00578##

(123) A mixture of 47.8 g (100 mmol) of 9,9-bis(6-bromopyrid-2-yl)fluorine [1323362-54-4], 69.1 g (230 mmol) of pinacolyl 1,1,3,3-tetramethylindane-5-boronate, S4-B, 42.4 g (400 mmol) of sodium carbonate, 1.2 g (1 mmol) of tetrakistriphenylphosphinopalladium(0), 300 ml of toluene, 200 ml of dioxane and 300 ml of water is heated under reflux for 30 h. After cooling, the organic phase is separated off, filtered through a Celite bed, with the Celite being rinsed with 300 ml of toluene, the combined filtrates are washed three times with 300 ml of water each time, dried over magnesium sulfate and then freed from toluene in vacuo. The residue is recrystallised three times from ethanol with addition of a little ethyl acetate and finally freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.5 mbar, T about 310 C.). Yield: 36.6 g (55 mmol), 55%; purity: about 99.5% according to .sup.1H-NMR.

(124) The following compounds can be prepared analogously:

(125) TABLE-US-00025 Starting Ex. Starting material material Product Yield L140 0 56% L141 58% L142 54% L143 0 57% L144 32% L145 47% L146 53%

Example L147

Tetradentate Ligands

(126) ##STR00600##

(127) 20 ml (50 mmol) of n-BuLi, 2.5 M in n-hexane, are added dropwise to a vigorously stirred solution, cooled to 78 C., of 15.0 g (50 mmol) of 4-(3-bromophenyl)-3-azatricyclo[6.2.1.0*2,7*]undeca-2(7),3,5-triene [1421789-46-9] in 200 ml of THF, and the mixture is then stirred at 78 C. for a further 1 h. A mixture of 13.9 ml (60 mmol) of triisopropyl borate and 30 ml of THF is then added in one portion, the mixture is stirred at 78 C. for a further 1 h and then allowed to warm to room temperature. 200 ml of toluene, 200 ml of saturated sodium hydrogencarbonate solution, 13.8 g (55 mmol) of 2-(6-bromopyridin-2-yl)phenol [1394900-18-5], 1.2 g (1 mmol) of tetrakistriphenylphosphinopalladium(0) are added to the reaction mixture, which is then heated under reflux for 16 h. After cooling, 200 ml of saturated ammonium chloride solution and 300 ml of ethyl acetate are added, the aqueous phase is separated off, the organic phase is filtered through a Celite bed, the latter is rinsed with 200 ml of ethyl acetate, the combined filtrates are washed three times with water and once with saturated sodium chloride solution and dried over magnesium sulfate. The oily residue obtained after removal of the solvent is recrystallised three times from ethanol with addition of a little ethyl acetate and finally freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.5 mbar, T about 270 C.). Yield: 7.0 g (18 mmol), 36%; purity: about 99.5% according to 1H-NMR.

Example L148

Tetradentate Ligands

(128) ##STR00601##

(129) Procedure analogous to C. Cao et al., Synth. Commun. 2012, 42, 380. A mixture of 15.9 g (50 mmol) of 5,5,6,6,7,7-hexamethyl-1-phenyl-1,5,6,7-tetrahydroindeno[5,6-d]imidazole, L78 B), and 4.7 g (25 mmol) of 1,2-dibromoethane [106-93-4] is heated at 120 C. for 6 h in an autoclave. After cooling, the solid mass is taken up in 100 ml of tert-butyl methyl ether, homogenised with stirring, the white solid is filtered off, washed twice with 50 ml of tert-butyl methyl ether each time and dried in vacuo. Yield: 18.1 g (22 mmol), 88%; purity: about 98.0% according to .sup.1H-NMR.

(130) The following compounds can be prepared analogously:

(131) TABLE-US-00026 Ex. Imidazole Ligand Yield L149 02 03 86% L150 04 05 83% L151 06 07 91% L152 08 09 87% L153 0 74%

Example L154

Hexadentate Ligands

(132) ##STR00612##

(133) A mixture of 51.4 g (100 mmol) of tris(6-bromopyridin-2-yl)methoxymethane [336158-91-9], 99.1 g (330 mmol) of pinacolyl 1,1,3,3-tetramethylindane-5-boronate, 84-B, 42.4 g (400 mmol) of sodium carbonate, 1.2 g (1 mmol) of tetrakistriphenylphosphinopalladium(0), 500 ml of toluene, 300 ml of dioxane and 500 ml of water is heated under reflux for 36 h. After cooling, the organic phase is separated off, filtered through a Celite bed, with the Celite being rinsed with 400 ml of toluene, the combined filtrates are washed three times with 300 ml of water each time, dried over magnesium sulfate and then freed from toluene in vacuo. The residue is recrystallised three times from isopropanol with addition of a little ethyl acetate and finally freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.5 mbar, T about 310 C.). Yield: 40.5 g (51 mmol), 51%; purity: about 99.5% according to .sup.1H-NMR.

(134) The following compounds can be prepared analogously:

(135) TABLE-US-00027 Starting Ex. Starting material material Product Yield L155 48% L156 47%

Example L157

Hexadentate Ligands

(136) ##STR00619##

(137) Procedure analogous to L148, where the 1,2-dibromoethane is replaced by 5.2 g (16.7 mmol) of 1,1,1-tris(bromomethyl)ethane [60111-68-4]. Yield: 19.0 g (15 mmol), 90%; purity: about 99.0% according to .sup.1H-NMR.

(138) The following compound can be prepared analogously:

(139) ##STR00620##

(140) 1,1,1-Tris(bromomethyl)ethane is replaced by 6.1 g (16.7 mmol) of cis,cis-1,2,3-cyclopropanetrimethanol trimethanesulfonate [945230-85-3]. Yield: 15.9 g (12 mmol), 72%; purity: about 99.0% according to 1H-NMR.

C: Synthesis of the Metal Complexes

(141) 1) Homoleptic Tris-Facial Iridium Complexes of the Phenylpyridine, Phenylimidazole or Phenylbenzimidazole Type:

(142) Variant A: Trisacetylacetonatoiridium(III) as Iridium Starting Material

(143) A mixture of 10 mmol of trisacetylacetonatoiridium(III) [15635-87-7] and 60 mmol of the ligand L and a glass-clad magnetic stirrer bar are melted into a thick-walled 50 ml glass ampoule in vacuo (10.sup.5 mbar). The ampoule is heated at the temperature indicated for the time indicated, during which the molten mixture is stirred with the aid of a magnetic stirrer. In order to prevent sublimation of the ligands onto relatively cold parts of the ampoule, the entire ampoule must have the temperature indicated. Alternatively, the synthesis can be carried out in a stirred autoclave with glass insert. After cooling (NOTE: the ampoules are usually under pressure!), the ampoule is opened, the sinter cake is stirred for 3 h with 100 g of glass beads (diameter 3 mm) in 100 ml of a suspension medium (the suspension medium is selected so that the ligand is readily soluble, but the metal complex has low solubility therein, typical suspension media are methanol, ethanol, dichloromethane, acetone, THF, ethyl acetate, toluene, etc.) and mechanically digested in the process. The fine suspension is decanted off from the glass beads, the solid is filtered off with suction, rinsed with 50 ml of the suspension medium and dried in vacuo. The dry solid is placed on a 3-5 cm deep aluminium oxide bed (aluminium oxide, basic, activity grade 1) in a continuous hot extractor and then extracted with an extractant (initially introduced amount about 500 ml, the extractant is selected so that the complex is readily soluble therein at elevated temperature and has low solubility therein when cold, particularly suitable extractants are hydrocarbons, such as toluene, xylenes, mesitylene, naphthalene, o-dichlorobenzene, halogenated aliphatic hydrocarbons are generally unsuitable since they may halogenate or decompose the complexes). When the extraction is complete, the extractant is evaporated to about 100 ml in vacuo. Metal complexes which have excessively good solubility in the extractant are brought to crystallisation by dropwise addition of 200 ml of methanol. The solid of the suspensions obtained in this way is filtered off with suction, washed once with about 50 ml of methanol and dried. After drying, the purity of the metal complex is determined by means of NMR and/or HPLC. If the purity is below 99.5%, the hot extraction step is repeated, omitting the aluminium oxide bed from the 2nd extraction. When a purity of 99.5-99.9% has been reached, the metal complex is heated or sublimed. The heating is carried out in a high vacuum (p about 10.sup.6 mbar) in the temperature range from about 200-300 C. The sublimation is carried out in a high vacuum (p about 10.sup.6 mbar) in the temperature range from about 230-400 C., with the sublimation preferably being carried out in the form of a fractional sublimation. Complexes which are readily soluble in organic solvents may alternatively also be chromatographed on silica gel.

(144) If ligands in point group C1 are employed in the form of a racemic mixture, the derived fac-metal complexes are produced in the form of a diastereomer mixture. The enantiomer pair , in point group C3 generally has significantly lower solubility in the extractant than that in point group Cl, which is consequently enriched in the mother liquor. Separation of the diastereomers by this method is frequently possible. In addition, the diastereomers can also be separated by chromatography. If ligands in point group Cl are employed in enantiomerically pure form, the enantiomer pair , in point group C3 is formed.

(145) Variant B: Tris-(2,2,6,6-tetramethyl-3,5-heptanedionato)iridium(III) as iridium starting material

(146) Procedure analogous to variant A, using 10 mmol of tris(2,2,6,6-tetramethyl-3,5-heptanedionato)iridium [99581-86-9] instead of 10 mmol of trisacetylacetonatoiridium(III) [15635-87-7]. The use of this starting material is advantageous since the purity of the crude products obtained is frequently better than in the case of variant A. In addition, the build-up of pressure in the ampoule is frequently not so pronounced.

(147) Variant C: Sodium [cis,trans-dichloro(bisacetylacetonato)]iridate(III) as iridium starting material

(148) A mixture of 10 mmol of sodium [cis,trans-dichloro(bisacetylacetonato)]-iridate(III) [876296-21-8] and 60 mmol of the ligand in 50 ml of ethylene glycol, propylene glycol or diethylene glycol is heated under gentle reflux under a gentle stream of argon for the time indicated. After cooling to 60 C., the reaction mixture is diluted with a mixture of 50 ml of ethanol and 50 ml of 2 N hydrochloric acid with stirring and stirred for a further 1 h, the precipitated solid is filtered off with suction, washed three times with 30 ml of ethanol each time and then dried in vacuo. Purification by hot extraction or chromatography and fractional sublimation, as described under A.

(149) TABLE-US-00028 Variant Reaction medium Reaction temp. Reaction time Ligand Ir complex Suspension medium Ex. L Diastereomer Extractant Yield Ir(L1).sub.3 L1 C Propylene glycol Reflux 100 h o-Xylene 43% Ir(L2).sub.3 L2 Ir(L2).sub.3 as Ir(L1).sub.3 38% Ir(L3).sub.3 L3 A 230 C. 100 h Acetone o-Xylene 42% Ir(L4).sub.3 L4 Ir(L4).sub.3 as Ir(L1).sub.3 44% Ir(L5).sub.3 L5 A 280 C. 130 h Acetone o-Xylene 38% Ir(L6).sub.3 L6 C Propylene glycol Reflux 130 h o-Xylene 39% Ir(L7).sub.3 L7 B 240 C. 130 h Acetone o-Xylene 28% Ir(L8).sub.3 L8 Ir(L8).sub.3 as Ir(L1).sub.3 44% Ir(L9).sub.3 L9 as Ir(L6).sub.3 28% Ir(L10).sub.3 L10 B 250 C. 130 h Acetone o-Xylene 22% Ir(L11).sub.3 L11 B 230 C. 130 h Acetone o-Xylene 23% Ir(L12).sub.3 L12 Ir(L12).sub.3 as Ir(L1).sub.3 38% Ir(L13).sub.3 L13 Ir(L13).sub.3 as Ir(L1).sub.3 35% Ir(L15).sub.3 L15 A 230 C. 100 h Acetone o-Xylene 28% Ir(L16).sub.3 L16 0 C Ethylene glycol Reflux 140 h Chromatographic purification 34% Ir(L17).sub.3 L17 B 210 C. 100 h Acetone o-Xylene 26% Ir(L18).sub.3 L18 Ir(L18).sub.3 as Ir(L9).sub.3 31% ,-C3 Ir(L19).sub.3 L19 Ir(L19).sub.3 as Ir(L9).sub.3 26% ,-C3 Ir(L20).sub.3 L20 Ir(L20).sub.3 as Ir(L1).sub.3 20% Ir(L22).sub.3 L22 C Propylene glycol Reflux 130 h o-Xylene 26% Ir(L23).sub.3 L23 C Propylene glycol Reflux 120 h o-Xylene 24 & Ir(L24).sub.3 L24 Ir(L24).sub.3 as Ir(L22).sub.3 25% ,-C3 Ir(L25).sub.3 L25 as Ir(L16).sub.3 23% Ir(L26).sub.3 L26 Ir(L26).sub.3 C 25% ,-C3 Diethylene glycol 220 C. 140 h Chrom. purification Metal complex is heated Ir(L27).sub.3 L27 Ir(L27).sub.3 as Ir(L22).sub.3 27% ,-C3 Ir(L28).sub.3 L28 B 230 C. 130 h Acetone o-Xylene 26% Ir(L29).sub.3 L29 as Ir(L28).sub.3 24% Ir(L30).sub.3 L30 as Ir(L28).sub.3 25% Ir(L31).sub.3 L31 Ir(L31).sub.3 as Ir(L28).sub.3 19% ,-C3 Ir(L32).sub.3 L32 as Ir(L26).sub.3 23% Ir(L33).sub.3 L33 as Ir(L3).sub.3 27% Ir(L34).sub.3 L34 as Ir(L34).sub.3 as Ir(L3).sub.3 24% ,-C3 Ir(L35).sub.3 L35 0 as Ir(L11).sub.3 46% Ir(L36).sub.3 L36 as Ir(L11).sub.3 16% Ir(L37).sub.3 L37 C Ethylene glycol Reflux 140 h Chromatographic purification 24% Ir(L38).sub.3 L38 as Ir(L11).sub.3 39% Ir(L39).sub.3 L39 C Diethylene glycol Reflux 130 h Chromatographic purification 23% Ir(L40).sub.3 L40 C Diethylene glycol Reflux 130 h Chromatographic purification 19% Ir(L41).sub.3 L41 C Diethylene glycol Reflux 130 h Chromatographic purification 26% Ir(L42).sub.3 L42 as Ir(L1).sub.3 50% Ir(L43).sub.3 L43 as Ir(L42).sub.3 as Ir(L42).sub.3 54% Ir(L44).sub.3 L44 as Ir(L16).sub.3 47% Ir(L45).sub.3 L45 as Ir(L44).sub.3 as Ir(L44).sub.3 48% Ir(L46).sub.3 L46 B 220 C. 130 h Acetone o-Xylene 44% Ir(L47).sub.3 L47 0 A 230 C. 130 h Acetone o-Xylene 45% Ir(L48).sub.3 L48 A 230 C. 150 h Acetone o-Xylene 43% Ir(L49).sub.3 L49 as Ir(L48).sub.3 23% Ir(L50).sub.3 L50 Ir(L50).sub.3 as Ir(L48).sub.3 27% ,-C3 Ir(L51).sub.3 L51 Ir(L51).sub.3 as Ir(L42).sub.3 38% ,-C3 Ir(L52).sub.3 L52 as Ir(L48).sub.3 25% Ir(L64).sub.3 L64 B 240 C. 120 h Acetone o-Xylene 48% Ir(L65).sub.3 L65 Ir(L65).sub.3 as Ir(L64).sub.3 42% Ir(L66).sub.3 L66 Ir(L66).sub.3 as Ir(L64).sub.3 45% Ir(L67).sub.3 L67 Ir(L67).sub.3 as Ir(L64).sub.3 39% Ir(L68).sub.3 L68 B 240 C. 130 h Acetone o-Xylene 26% Ir(L69).sub.3 L69 Ir(L69).sub.3 as Ir(L68).sub.3 16% ,-C3 Ir(L70).sub.3 L70 Ir(L70).sub.3 as Ir(L68).sub.3 37% Ir(L71).sub.3 L71 Ir(L71).sub.3 as Ir(L68).sub.3 21% ,-C3 Ir(L72).sub.3 L72 B 260 C. 150 h Acetone o-Xylene 22% Ir(L73).sub.3 L73 as Ir(L68).sub.3 23% Ir(L74).sub.3 L74 B 245 C. 130 h Acetone o-Xylene 38% Ir(L75).sub.3 L75 Ir(L75).sub.3 as Ir(L74).sub.3 31% ,-C3 Ir(L76).sub.3 L76 B 260 C. 140 h Acetone o-Xylene 28% Ir(L77).sub.3 L77 0 as Ir(L74).sub.3 34% Ir(L95).sub.3 L95 A 250 C. 40 h Ethanol Cyclohexane 33% Ir(L97).sub.3 L97 Ir(L97).sub.3 as Ir(L95).sub.3 30% ,-C3 + C1 Ir(L98).sub.3 L98 Ir(L98).sub.3 as Ir(L95).sub.3 26% ,-C3 + C1 Ir(L99).sub.3 L99 Ir(L99).sub.3 as Ir(L95).sub.3 23% ,-C3 + C1 Ir(L101).sub.3 L101 Ir(L101).sub.3 as Ir(L95).sub.3 39% Ir(L102).sub.3 L102 A 270 C. 60 h Ethanol Cyclohexane 3.6% Ir(L128).sub.3 L128 B 250 C. 40 h Ethanol Cyclohexane/ethyl acetate 8/2, v:v 34% Ir(L129).sub.3 L129 as Ir(L128).sub.3 35% Ir(L130).sub.3 L130 Ir(L130).sub.3 B 28% 260 C. 40 h Ethanol Cyclohexane/ethyl acetate 8/2, v:v Ir(L131).sub.3 L131 Ir(L131).sub.3 as Ir(L128).sub.3 8% Ir(L132).sub.3 L132 Ir(L132).sub.3 as Ir(L128).sub.3 32% Ir(L133).sub.3 L133 Ir(L133).sub.3 as Ir(L128).sub.3 25% ,-C3 + C1 Ir(L134).sub.3 L134 Ir(L134).sub.3 as Ir(L128).sub.3 26% Ir(L135).sub.3 L135 Ir(L135).sub.3 as Ir(L130).sub.3 20% ,-C3 + C1
2) Homoleptic Iridium Complexes of the Arduengo Carbene Type:

(150) Preparation analogous to K. Tsuchiya, et al., Eur. J. Inorg. Chem., 2010, 926.

(151) A mixture of 10 mmol of the ligand, 3 mmol of iridium(III) chloride hydrate, 10 mmol of silver carbonate, 10 mmol of sodium carbonate in 75 ml of 2-ethoxyethanol is warmed under reflux for 24 h. After cooling, 300 ml of water are added, the precipitated solid is filtered off with suction, washed once with 30 ml of water and three times with 15 ml of ethanol each time and dried in vacuo. The fac/mer isomer mixture obtained in this way is chromatographed on silica gel. The isomers obtained in this way are subjected to fractional sublimation as described under 1) variant A.

(152) TABLE-US-00029 Ligand Ir complex Ex. L Diastereomer Yield fac-Ir (L78).sub.3 mer-Ir (L78).sub.3 L78 36% 17% fac-Ir L79 fac-Ir(L79).sub.3 11% (L79).sub.3 mer-Ir mer-Ir(L79).sub.3 24% (L79).sub.3 fac-Ir (L80).sub.3 mer-Ir (L80).sub.3 L80 44% 11% fac-Ir (L81).sub.3 mer-Ir (L81).sub.3 L81 38% 17% fac-Ir (L82).sub.3 mer-Ir (L82).sub.3 L82 23% fac-Ir (L83).sub.3 mer-Ir (L83).sub.3 L83 34% 12% fac-Ir (L84).sub.3 mer-Ir (L84).sub.3 L84 0 12% 16% fac-Ir (L85).sub.3 mer-Ir (L85).sub.3 L85 25% fac-Ir (L86).sub.3 mer-Ir (L86).sub.3 L86 33% 12% fac-Ir (L87).sub.3 mer-Ir (L87).sub.3 L87 6% 13% fac-Ir (L88).sub.3 mer-Ir (L88).sub.3 L88 19% 15% fac-Ir (L89).sub.3 mer-Ir (L89).sub.3 L89 24% 9% fac-Ir (L90).sub.3 mer-Ir (L90).sub.3 L90 26% 11% fac-Ir (L91).sub.3 mer-Ir (L91).sub.3 L91 18% fac-Ir (L92).sub.3 mer-Ir (L92).sub.3 L92 16%
3) Iridium Complexes of the [Ir(L).sub.2Cl].sub.2 Type
Variant A:

(153) A mixture of 22 mmol of the ligand, 10 mmol of iridium(III) chloride hydrate, 75 ml of 2-ethoxyethanol and 25 ml of water is heated under reflux for 16 24 h with vigorous stirring. If the ligand does not dissolve or does not dissolve completely in the solvent mixture under reflux, 1,4-dioxane is added until a solution has formed. After cooling, the precipitated solid is filtered off with suction, washed twice with ethanol/water (1:1, vv) and then dried in vacuo. The chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 obtained in this way is reacted further without purification.

(154) Variant B:

(155) A mixture of 10 mmol of sodium bisacetylacetonatodichloroiridate(III) [770720-50-8], 24 mmol of ligand L and a glass-clad magnetic stirrer bar are melted into a thick-walled 50 ml glass ampoule in vacuo (10.sup.5 mbar). The ampoule is heated at the temperature indicated for the time indicated, during which the molten mixture is stirred with the aid of a magnetic stirrer. After coolingNOTE: the ampoules are usually under pressure! the ampoule is opened, the sinter cake is stirred for 3 h with 100 g of glass beads (diameter 3 mm) in 100 ml of the suspension medium indicated (the suspension medium is selected so that the ligand is readily soluble, but the chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 has low solubility therein, typical suspension media are dichloromethane, acetone, ethyl acetate, toluene, etc.) and mechanically digested at the same time. The fine suspension is decanted off from the glass beads, the solid [Ir(L).sub.2Cl].sub.2 which still contains about 2 eq. of NaCl, referred to below as the crude chloro dimer) is filtered off with suction and dried in vacuo. The crude chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 obtained in this way is reacted further without purification.

(156) TABLE-US-00030 Ir complex Variant Ligand Temp./time Ex. L Diastereomer Yield [Ir(L1).sub.2Cl].sub.2 L1 76% [Ir(L2).sub.2Cl].sub.2 L2 Ir[L2)Cl].sub.2 81% A [Ir(L5).sub.2Cl].sub.2 L5 0 61% [Ir(L6).sub.2Cl].sub.2 L6 Ir[(L6)Cl].sub.2 74% A [Ir(L10).sub.2Cl].sub.2 L10 63% [Ir(L11).sub.2Cl].sub.2 L11 69% [Ir(L12).sub.2Cl].sub.2 L12 Ir[(L12)Cl].sub.2 75% B [Ir(L14).sub.2Cl].sub.2 L14 [Ir(L21).sub.2Cl].sub.2 L21 Ir[(L21)Cl].sub.2 53% A Diastereomer mixture [Ir(L25).sub.2Cl].sub.2 L25 73% [Ir(L42).sub.2Cl].sub.2 L42 84% [Ir(L47).sub.2Cl].sub.2 L47 80% [Ir(L48).sub.2Cl].sub.2 L48 78% [Ir(L53).sub.2Cl].sub.2 L53 46% [Ir(L55).sub.2Cl].sub.2 L55 Ir[(L55)Cl].sub.2 44% A [Ir(L59).sub.2Cl].sub.2 L59 57% [Ir(L60).sub.2Cl].sub.2 L60 0 63% [Ir(L62).sub.2Cl].sub.2 L62 65% [Ir(L64).sub.2Cl].sub.2 L64 88% [Ir(L72).sub.2Cl].sub.2 L72 78% [Ir(L74).sub.2Cl].sub.2 L74 66% [Ir(L95).sub.2Cl].sub.2 L95 88% [Ir(L96).sub.2Cl].sub.2 L96 [Ir(L96).sub.2Cl].sub.2 86% as [Ir(L95).sub.2Cl].sub.2 [Ir(L100).sub.2Cl].sub.2 L100 [Ir(L100).sub.2Cl].sub.2 87% as [Ir(L95).sub.2Cl].sub.2 [Ir(L102).sub.2Cl].sub.2 L102 92% [Ir(L103).sub.2Cl].sub.2 L103 [Ir(L103).sub.2Cl].sub.2 90% as [Ir(L102).sub.2Cl].sub.2 [Ir(L104).sub.2Cl].sub.2 L104 [Ir(L104).sub.2Cl].sub.2 90% as [Ir(L102).sub.2Cl].sub.2 [Ir(L105).sub.2Cl].sub.2 L105 [Ir(L105).sub.2Cl].sub.2 83% as [Ir(L102).sub.2Cl].sub.2 [Ir(L106).sub.2Cl].sub.2 L106 [Ir(L106).sub.2Cl].sub.2 91% as [Ir(L102).sub.2Cl].sub.2 [Ir(L107).sub.2Cl].sub.2 L107 [Ir(L107).sub.2Cl].sub.2 90% as [Ir(L102).sub.2Cl].sub.2 [Ir(L108).sub.2Cl].sub.2 L108 [Ir(L108).sub.2Cl].sub.2 87% as [Ir(L102).sub.2Cl].sub.2 [Ir(L109).sub.2Cl].sub.2 L109 [Ir(L109).sub.2Cl].sub.2 90% as [Ir(L102).sub.2Cl].sub.2 [Ir(L110).sub.2Cl].sub.2 L110 [Ir(L110).sub.2Cl].sub.2 92% as [Ir(L102).sub.2Cl].sub.2 [Ir(L111).sub.2Cl].sub.2 L111 [Ir(L111).sub.2Cl].sub.2 89% as [Ir(L102).sub.2Cl].sub.2 [Ir(L112).sub.2Cl].sub.2 L112 [Ir(L112).sub.2Cl].sub.2 84% as [Ir(L102).sub.2Cl].sub.2 [Ir(L113).sub.2Cl].sub.2 L113 [Ir(L113).sub.2Cl].sub.2 78% B 260 C./60 h Diastereomer mixture [Ir(L114).sub.2Cl].sub.2 L114 [Ir(L114).sub.2Cl].sub.2 64% B 280 C./60 h Diastereomer mixture [Ir(L115a).sub.2Cl].sub.2 L115a [Ir(L115a).sub.2Cl].sub.2 89% as [Ir(L102).sub.2Cl].sub.2 [Ir(L115b).sub.2Cl].sub.2 L115b [Ir(L115b).sub.2Cl].sub.2 91% as [Ir(L102).sub.2Cl].sub.2 [Ir(L116).sub.2Cl].sub.2 L116 [Ir(L116).sub.2Cl].sub.2 87% as [Ir(L114).sub.2Cl].sub.2 [Ir(L117).sub.2Cl].sub.2 L117 [Ir(L117).sub.2Cl].sub.2 88% as [Ir(L102).sub.2Cl].sub.2 [Ir(L118).sub.2Cl].sub.2 L118 [Ir(L118).sub.2Cl].sub.2 88% as [Ir(L102).sub.2Cl].sub.2 [Ir(L119).sub.2Cl].sub.2 L119 [Ir(L119).sub.2Cl].sub.2 90% as [Ir(L102).sub.2Cl].sub.2 [Ir(L120).sub.2Cl].sub.2 L120 [Ir(L120).sub.2Cl].sub.2 89% as [Ir(L102).sub.2Cl].sub.2 [Ir(L121).sub.2Cl].sub.2 L121 [Ir(L121).sub.2Cl].sub.2 89% as [Ir(L102).sub.2Cl].sub.2 [Ir(L122).sub.2Cl].sub.2 L122 [Ir(L122).sub.2Cl].sub.2 87% as [Ir(L102).sub.2Cl].sub.2 [Ir(L123).sub.2Cl].sub.2 L123 [Ir(L123).sub.2Cl].sub.2 93% as [Ir(L102).sub.2Cl].sub.2 [Ir(L124).sub.2Cl].sub.2 L124 [Ir(L124).sub.2Cl].sub.2 78% B 250 C./30 h Diastereomer mixture [Ir(L125).sub.2Cl].sub.2 L125 [Ir(L125).sub.2Cl].sub.2 80% as [Ir(L124).sub.2Cl].sub.2 [Ir(L126).sub.2Cl].sub.2 L126 [Ir(L126).sub.2Cl].sub.2 67% as [Ir(L124).sub.2Cl].sub.2 [Ir(L127).sub.2Cl].sub.2 L127 [Ir(L127).sub.2Cl].sub.2 69% B 260 C./28 h [Ir(L129).sub.2Cl].sub.2 L129 91% [Ir(L136).sub.2Cl].sub.2 L136 85% [Ir(L137).sub.2Cl].sub.2 L137 [Ir(L137).sub.2Cl].sub.2 86% as [Ir(L136).sub.2Cl].sub.2 [Ir(L138).sub.2Cl].sub.2 L138 [Ir(L138).sub.2Cl].sub.2 84% as [Ir(L136).sub.2Cl].sub.2
4) Iridium Complexes of the [Ir(L).sub.2(HOMe).sub.2]OTf Type

(157) 5 ml of methanol and then 10 mmol of silver(I) trifluoromethanesulfonate [2923-28-6] are added to a suspension of 5 mmol of the chloro dimer [Ir(L).sub.2Cl].sub.2 in 150 ml of dichloromethane, and the mixture is stirred at room temperature for 18 h. The precipitated silver(I) chloride is filtered off with suction via a Celite bed, the filtrate is evaporated to dryness, the yellow residue is taken up in 30 ml of toluene or cyclohexane, the solid is filtered off, washed with n-heptane and dried in vacuo. The product of the formula [Ir(L).sub.2(HOMe).sub.2]OTf obtained in this way is reacted further without purification.

(158) TABLE-US-00031 Ex. [Ir(L).sub.2Cl].sub.2 [Ir(L).sub.2(HOMe).sub.2]OTf Yield [Ir(L1).sub.2(HOMe).sub.2]OTf Ir[(L1)Cl].sub.2 81% [Ir(L2).sub.2(HOMe).sub.2]OTf [Ir(L2).sub.2Cl].sub.2 [Ir(L2).sub.2(HOMe).sub.2]OTf 79% [Ir(L5).sub.2(HOMe).sub.2]OTf [Ir(L5).sub.2Cl].sub.2 [Ir(L5).sub.2(HOMe).sub.2]OTf 77% [Ir(L6).sub.2(HOMe).sub.2]OTf [Ir(L6).sub.2Cl].sub.2 [Ir(L6).sub.2(HOMe).sub.2]OTf 77% [Ir(L10).sub.2(HOMe).sub.2]OTf [Ir(L10).sub.2Cl].sub.2 [Ir(L10).sub.2(HOMe).sub.2]OTf 80% [Ir(L11).sub.2(HOMe).sub.2]OTf [Ir(L11).sub.2Cl].sub.2 [Ir(L11).sub.2(HOMe).sub.2]OTf 76% [Ir(L12).sub.2(HOMe).sub.2]OTf [Ir(L12).sub.2Cl].sub.2 [Ir(L12).sub.2(HOMe).sub.2]OTf 64% [Ir(L14).sub.2(HOMe).sub.2]OTf [Ir(L14).sub.2Cl].sub.2 [Ir(L14).sub.2(HOMe).sub.2]OTf 82% [Ir(L21).sub.2(HOMe).sub.2]OTf [Ir(L21).sub.2Cl].sub.2 [Ir(L21).sub.2(HOMe).sub.2]OTf 79% [Ir(L25).sub.2(HOMe).sub.2]OTf [Ir(L25).sub.2Cl].sub.2 [Ir(L25).sub.2(HOMe).sub.2]OTf 80% [Ir(L42).sub.2(HOMe).sub.2]OTf [Ir(L42).sub.2Cl].sub.2 [Ir(L42).sub.2(HOMe).sub.2]OTf 75% [Ir(L47).sub.2(HOMe).sub.2]OTf [Ir(L47).sub.2Cl].sub.2 [Ir(L47).sub.2(HOMe).sub.2]OTf 86% [Ir(L48).sub.2(HOMe).sub.2]OTf [Ir(L48).sub.2Cl].sub.2 [Ir(L48).sub.2(HOMe).sub.2]OTf 78% [Ir(L53).sub.2(HOMe).sub.2]OTf [Ir(L53).sub.2Cl].sub.2 [Ir(L53).sub.2(HOMe).sub.2]OTf 81% [Ir(L55).sub.2(HOMe).sub.2]OTf [Ir(L55).sub.2Cl].sub.2 [Ir(L55).sub.2(HOMe).sub.2]OTf 82% [Ir(L59).sub.2(HOMe).sub.2]OTf [Ir(L59).sub.2Cl].sub.2 [Ir(L59).sub.2(HOMe).sub.2]OTf 80% [Ir(L60).sub.2(HOMe).sub.2]OTf [Ir(L60).sub.2Cl].sub.2 [Ir(L60).sub.2(HOMe).sub.2]OTf 78% [Ir(L62).sub.2(HOMe).sub.2]OTf [Ir(L62).sub.2Cl].sub.2 [Ir(L62).sub.2(HOMe).sub.2]OTf 77% [Ir(L64).sub.2(HOMe).sub.2]OTf [Ir(L64).sub.2Cl].sub.2 [Ir(L64).sub.2(HOMe).sub.2]OTf 76% [Ir(L72).sub.2(HOMe).sub.2]OTf [Ir(L72).sub.2Cl].sub.2 [Ir(L72).sub.2(HOMe).sub.2]OTf 79% [Ir(L74).sub.2(HOMe).sub.2]OTf [Ir(L74).sub.2Cl].sub.2 [Ir(L74).sub.2(HOMe).sub.2]OTf 83% [Ir(L95).sub.2(HOMe).sub.2]OTf [Ir(L95).sub.2Cl].sub.2 [Ir(L95).sub.2(HOMe).sub.2]OTf 83% [Ir(L96).sub.2(HOMe).sub.2]OTf [Ir(L96).sub.2Cl].sub.2 [Ir(L96).sub.2(HOMe).sub.2]OTf 77% [Ir(L100).sub.2(HOMe).sub.2]OTf [Ir(L100).sub.2Cl].sub.2 [Ir(L100).sub.2(HOMe).sub.2]OTf 74% [Ir(L102).sub.2(HOMe).sub.2]OTf [Ir(L102).sub.2Cl].sub.2 [Ir(L102).sub.2(HOMe).sub.2]OTf 76% [Ir(L129).sub.2(HOMe).sub.2]OTf [Ir(L129).sub.2Cl].sub.2 [Ir(L129).sub.2(HOMe).sub.2]OTf 86%
5) Heteroleptic Tris-Facial Iridium Complexes of the Phenylpyridine, Phenylimidazole or Phenylbenzimidazole Type:

(159) A mixture of 10 mmol of the ligand L, 10 mmol of bis(methanol)bis[2-(2-pyridinyl-N)phenyl-C]iridium(III) trifluoromethanesulfonate [1215692-14-0] or bis(methanol)bis[2-(6-methyl-2-pyridinyl-N)phenyl-C]iridium(III) trifluoromethanesulfonate [1215692-29-7] or iridium complexes of the [Ir(L).sub.2(HOMe).sub.2]OTf type according to the invention, 11 mmol of 2,6-dimethylpyridine and 150 ml of ethanol is heated under reflux for 40 h. After cooling, the precipitated solid is filtered off with suction, washed three times with 30 ml of ethanol each time and dried in vacuo. The crude product obtained in this way is chromatographed on silica gel (solvent or mixtures thereof, for example DCM, THF, toluene, n-heptane, cyclohexane) and subjected to fractional sublimation as described under 1) variant A.

(160) TABLE-US-00032 [Ir(L).sub.2(HOMe).sub.2]OTf Ir complex Ex. Ligand L Diastereomer Yield Ir500 1215692-14-0 L1 00 46% Ir501 1215692-14-0 L2 01 48% Ir502 1215692-29-7 L17 02 43% Ir503 1215692-29-7 L24 03 45% Ir504 1215692-14-0 L36 04 24% Ir505 1215692-14-0 L42 05 56% Ir506 1215692-14-0 L48 06 51% Ir507 1215692-14-0 L54 07 38% IR508 1215692-14-0 L57 08 40% Ir509 1215692-14-0 L61 09 45% Ir510 1215692-14-0 L63 0 41% Ir511 1215692-29-7 L69 37% Ir512 1215692-29-7 L75 39% Ir513 [Ir(L1).sub.2HOMe)].sub.2]OTf 1008-89-56 43% Ir514 [Ir(L2).sub.2HOMe)].sub.2]OTf 1008-89-56 41% Ir515 [Ir(L5).sub.2HOMe)].sub.2]OTf 612-96-4 39% Ir516 [Ir(L6).sub.2HOMe)].sub.2]OTf 1008-89-56 40% Ir517 [Ir(L10).sub.2HOMe)].sub.2]OTf L42 45% IrL518 [Ir(L11).sub.2HOMe)].sub.2]OTf L44 33% IrL519 [Ir(L12).sub.2HOMe)].sub.2]OTf 230-27-3 28% IrL520 [Ir(L14).sub.2HOMe)].sub.2]OTf 156021-08-8 0 46% Ir521 [I[(L21).sub.2HOMe)].sub.2]OTf 1008-89-56 26% Ir522 [Ir(L25).sub.2HOMe)].sub.2]OTf 10273-90-2 42% Ir523 [Ir(L42).sub.2HOMe)].sub.2]OTf 10273-90-2 40% Ir524 [Ir(L47).sub.2HOMe)].sub.2]OTf 80635-91-2 39% Ir525 [Ir(L48).sub.2HOMe)].sub.2]OTf 10273-90-2 46% Ir526 [Ir(L53).sub.2HOMe)].sub.2]OTf 1008-89-56 25% Ir527 [Ir(L55).sub.2HOMe)].sub.2]OTf 230-27-3 27% Ir528 [Ir(L59).sub.2HOMe)].sub.2]OTf 458541-39-4 33% Ir529 [Ir(L60).sub.2HOMe)].sub.2]OTf 1008-89-56 36% Ir530 [Ir(L62).sub.2HOMe)].sub.2]OTf 612-96-4 0 46% Ir531 [Ir(L64).sub.2HOMe)].sub.2]OTf 1008-89-56 43% Ir532 [Ir(L72).sub.2HOMe)].sub.2]OTf L74 37% Ir533 [Ir(L74).sub.2HOMe)].sub.2]OTf L75 35% Ir534 [Ir(L74).sub.2HOMe)].sub.2]OTf L93 21% Ir535 [Ir(L74).sub.2HOMe)].sub.2]OTf L94 19% Ir536 [Ir(L74).sub.2HOMe)].sub.2]OTf 22 mmol of L94 Solvent 1,2-propylene glycol 160 C. 26% Ir548 [Ir(L95).sub.2(HOMe).sub.2]OTf 1008-89-56 39% Ir549 [Ir(L96)2(HOMe).sub.2]OTf 458541-39-4 36% Ir550 [Ir(L100).sub.2(HOMe).sub.2]OTf 1008-89-56 22% Ir551 [Ir(L102).sub.2(HOMe).sub.2]OTf 1008-89-56 Solvent 1,2-propylene glycol 140 C. 0 26% Ir552 [Ir(L129).sub.2(HOMe).sub.2]OTf 156021-08-8 42%
6) Heteroleptic Tris-Facial Iridium Complexes Containing Ligands of the Arduengo Carbene Type:

(161) Preparation analogous to A. G. Tennyson et al., Inorg. Chem., 2009, 48, 6924.

(162) A mixture of 22 mmol of the ligand, 10 mmol of iridium chloro dimer [Ir(L).sub.2Cl].sub.2, 10 mmol of silver(l) oxide and 300 ml of 1,2-dichloroethane is stirred at 90 C. for 30 h. After cooling, the precipitated solid is filtered off with suction via a Celite bed, washed once with 30 ml of 1,2-dichloroethane, and the filtrate is evaporated to dryness in vacuo. The crude product obtained in this way is chromatographed on silica gel (solvent or mixtures thereof, for example dichloromethane, THF, toluene, n-heptane, cyclohexane) and subjected to fractional sublimation as described under 1) variant A.

(163) TABLE-US-00033 [Ir(L).sub.2Cl].sub.2 Ir complex Ex. Ligand L Diastereomer Yield Ir537 [Ir(PPy).sub.2Cl].sub.2 603109-48-4 L78 56% Ir538 [Ir(PPy).sub.2Cl].sub.2 603109-48-4 L81 41% Ir539 [Ir(L64).sub.2Cl].sub.2 L79 44% Ir540 [Ir(L74).sub.2Cl].sub.2 L86 39% Ir541 [Ir(L74).sub.2Cl].sub.2 L91 21%
7) Iridium Complexes of the Ir(L).sub.2L Type Containing Non-o-Metallated Ligands L:

(164) A mixture of 25 mmol of the ligand L, 10 mmol of iridium chloro dimer [Ir(L).sub.2Cl].sub.2, 30 mmol of sodium hydrogencarbonate, 100 ml of 2-ethoxyethanol and 30 ml of water is stirred at 90 C. for 16 h. After cooling, the precipitated solid is filtered off with suction, washed three times with 30 ml of ethanol each time and dried in vacuo. The crude product obtained in this way is chromatographed on silica gel (solvent or mixtures thereof, for example dichloromethane, THF, toluene, n-heptane, cyclohexane) or recrystallised, and subjected to fractional sublimation as described under 1) variant A.

(165) TABLE-US-00034 [Ir(L).sub.2Cl].sub.2 Ir complex Ex. Ligand L' Diastereomer Yield Ir542 [Ir(L1).sub.2Cl].sub.2 123-54-6 66% Ir543 [Ir(L5).sub.2Cl].sub.2 123-54-6 70% Ir544 [Ir(L10).sub.2Cl].sub.2 1118-71-4 58% Ir545 [Ir(L53).sub.2Cl].sub.2 123-54-6 0 60% Ir546 [Ir(L62).sub.2Cl].sub.2 123-54-6 58% Ir547 [Ir(L74).sub.2Cl].sub.2 98-98-6 71% Ir553 [Ir(L95).sub.2Cl].sub.2 123-54-6 76% Ir554 [Ir(L96).sub.2Cl].sub.2 123-54-6 77% Ir555 [Ir(L100).sub.2Cl].sub.2 123-54-6 67% Ir556 [Ir(L102).sub.2Cl].sub.2 123-54-6 70% Ir557 [Ir(L103).sub.2Cl].sub.2 123-54-6 28% Ir558 [Ir(L104).sub.2Cl].sub.2 123-54-6 58% Ir559 [Ir(L105).sub.2Cl].sub.2 123-54-6 66% Ir560 [Ir(L106).sub.2Cl].sub.2 123-54-6 0 63% Ir561 [Ir(L107).sub.2Cl].sub.2 123-54-6 76% Ir562 [Ir(L108).sub.2Cl].sub.2 123-54-6 35% Ir563 [Ir(L109).sub.2Cl].sub.2 123-54-6 35% Ir564 [Ir(L110).sub.2Cl].sub.2 123-54-6 73% Ir565 [Ir(L111).sub.2Cl].sub.2 123-54-6 75% Ir567 [Ir(L112).sub.2Cl].sub.2 123-54-6 67% Ir568 [Ir(L113).sub.2Cl].sub.2 123-54-6 70% Ir569 [Ir(L114).sub.2Cl].sub.2 123-54-6 58% Ir570 [Ir(L115a).sub.2Cl].sub.2 123-54-6 50% Ir571 [Ir(L115b).sub.2Cl].sub.2 123-54-6 0 70% Ir572 [Ir(L116).sub.2Cl].sub.2 123-54-6 48% Ir573 [Ir(L117).sub.2Cl].sub.2 123-54-6 67% It574 [Ir(L118).sub.2Cl].sub.2 123-54-6 59% It575 [Ir(L119).sub.2Cl].sub.2 123-54-6 56% Ir576 [Ir(L120).sub.2Cl].sub.2 123-54-6 60% Ir577 [Ir(L121).sub.2Cl].sub.2 123-54-6 46% Ir578 [Ir(L122).sub.2Cl].sub.2 123-54-6 55% Ir579 [Ir(L123).sub.2Cl].sub.2 123-54-6 43% Ir580 [Ir(L124).sub.2Cl].sub.2 123-54-6 47% Ir581 [Ir(L125).sub.2Cl].sub.2 123-54-6 0 32% Ir582 [Ir(L126).sub.2Cl].sub.2 123-54-6 45% Ir583 [Ir(L127).sub.2Cl].sub.2 123-54-6 56% Ir584 [Ir(L129).sub.2Cl].sub.2 123-54-6 80% Ir585 [Ir(L136).sub.2Cl].sub.2 123-54-6 51% Ir586 [Ir(L137).sub.2Cl].sub.2 123-54-6 33% Ir587 [Ir(L138).sub.2Cl].sub.2 123-54-6 37%
8) Platinum Complexes of the PtLL Type Containing Non-o-Metallated Ligands L:

(166) Preparation analogous to J. Brooks et al., Inorg. Chem. 2002, 41, 3055. A mixture of 20 mmol of the ligand L, 10 mmol of K.sub.2PtCl.sub.4, 75 ml of 2-ethoxyethanol and 25 ml of water is heated under reflux for 16 h. After cooling and addition of 100 ml of water, the precipitated solid is filtered off with suction, washed once with 30 ml of water and dried in vacuo. The platinum chloro dimer of the formula [PtLCl].sub.2 obtained in this way is suspended in 100 ml of 2-ethoxyethanol, 30 mmol of the ligands L and 50 mmol of sodium carbonate are added, the reaction mixture is stirred at 100 C. for 16 h and then evaporated to dryness in vacuo. The crude product obtained in this way is chromatographed on silica gel (solvent or mixtures thereof, for example dichloromethane, THF, toluene, n-heptane, cyclohexane) or recrystallised, and subjected to fractional sublimation as described under 1) variant A.

(167) TABLE-US-00035 Ligand L Ex. Ligand L Pt complex Yield Pt001 L1 123-54-6 36% Pt002 L10 1118-71-4 31% Pt003 L54 123-54-6 34% Pt004 L48 1118-71-4 0 29% Pt005 L64 98-98-6 33% Pt006 L74 77429-59-5 36%
9) Platinum Complexes of Tetradentate Ligands:

(168) A mixture of 10 mmol of the ligand L, 10 mmol of K.sub.2PtCl.sub.4, 400 mmol of lithium acetate, anhydrous, and 200 ml of glacial acetic acid is heated under reflux for 60 h. After cooling and addition of 200 ml of water, the mixture is extracted twice with 250 ml of toluene each time, dried over magnesium sulfate, filtered through a Celite bed, the Celite is rinsed with 200 ml of toluene, and the toluene is then removed in vacuo. The solid obtained in this way is purified as described under 1) variant A by hot extraction and then subjected to fractional sublimation.

(169) TABLE-US-00036 Ligand Ex. L Pt complex Extractant Yield Pt(L139) L139 Acetone 43% Pt(L140) L140 Pt(L140) Ethyl acetate 39% Cyclohexane 2:8, vv Pt(L141) L141 Pt(L141) as Pt(L140) 35% Pt(L142) L142 Pt(L142) as Pt(L140) 41% Pt(L143) L143 Pt(L143) Cyclohexane 40% Pt(L144) L144 Pt(L144) as Pt(L143) 29% Diastereomer mixture Pt(L145) L145 Pt(L145) as Pt(L143) 46% Pt(L146) L146 Pt(L146) as Pt(L143) 43% Pt(L147) L147 Pt(L147) o-Xylene 46%
10) Platinum Complexes of Tetradentate Ligands of the Arduengo Carbene Type:

(170) A mixture of 10 mmol of the ligand, 10 mmol of silver(I) oxide and 200 ml of dioxane is stirred at room temperature for 16 h, 100 ml of butanone, 20 mmol of sodium carbonate and 10 mmol of cyclooctadienylplatinum dichloride are then added, and the mixture is heated under reflux for 16 h. After removal of the solvent, the solid is extracted by stirring with 500 ml of hot toluene, the suspension is filtered through a Celite bed, and the filtrate is evaporated to dryness. The solid obtained in this way is chromatographed on silica gel with DCM and then subjected to fractional sublimation as described under 1) variant A.

(171) TABLE-US-00037 Ex. Ligand Complex Yield Pt(L148) L148 23% Pt(L149) L149 26% Pt(L150) L150 30% Pt(L151) L151 Diastereomer mixture 31% Pt(L152) L152 27% Pt(L153) L153 28%
11) Iridium Complexes of Hexadentate Ligands:

(172) A mixture of 10 mmol of the ligand L, 10 mmol of sodium bisacetylacetonatodichloroiridate(III) [770720-50-8] and 200 ml of triethylene glycol dimethyl ether is heated at 210 C. on a water separator for 48 h (the acetylacetone and thermal cleavage products of the solvent distil off). After cooling and addition of 200 ml of water, the precipitated solid is filtered off with suction and dried in vacuo. The solid is extracted by stirring with 500 ml of hot THF, the suspension is filtered through a Celite bed while still hot, the Celite is rinsed with 200 ml of THF, and the combined filtrates are evaporated to dryness. The solid obtained in this way is purified as described under 1) variant A by hot extraction with toluene and then subjected to fractional sublimation.

(173) TABLE-US-00038 Ex. Ligand Product Yield Ir(L154) L154 00 19% Ir(L155) L155 01 28% Ir(L156) L156 02 34%
12) Iridium Complexes of Hexadentate Ligands of the Arduengo Carbene Type:

(174) Preparation analogous to K. Tsuchiya et al., Eur. J. Inorg. Chem. 2010, 926.

(175) A mixture of 3 mmol of the ligand, 3 mmol of iridium(III) chloride hydrate, 10 mmol of silver carbonate and 10 mmol of sodium carbonate in 75 ml of 2-ethoxyethanol is warmed under reflux for 48 h. After cooling, 300 ml of water are added, the precipitated solid is filtered off with suction, washed once with 30 ml of water and three times with 15 ml of ethanol each time and dried in vacuo. The crude product obtained in this way is chromatographed on silica gel (DCM) and then subjected to fractional sublimation as described under 1) variant A.

(176) TABLE-US-00039 Ex. Ligand Product Yield Ir(L157) L157 03 22% Ir(L158) L158 04 26%
Derivatisation of the Metal Complexes
1) Halogenation of the Iridium Complexes:

(177) A10.5 mmol of N-halosuccinimide (halogen: Cl, Br, I) are added to a solution or suspension of 10 mmol of a complex carrying ACH groups (where A=1, 2 or 3) in the para-position to the iridium in 1000 ml of dichloromethane at 30 C. with exclusion of light and air, and the mixture is stirred for 20 h. Complexes which have low solubility in DCM can also be reacted in other solvents (TCE, THF, DMF, etc.) and at elevated temperature. The solvent is subsequently substantially removed in vacuo. The residue is boiled with 100 ml of MeOH, the solid is filtered off with suction, washed three times with 30 ml of methanol and then dried in vacuo.

Synthesis of Ir(L22-Br).SUB.3

(178) ##STR00805##

(179) 5.6 g (31.5 mmol) of N-bromosuccinimide are added in one portion to a suspension, stirred at 30 C., of 8.5 g (10 mmol) of Ir(L22).sub.3 in 1000 ml of DCM, and the mixture is then stirred for a further 20 h. After removal of about 900 ml of the DCM in vacuo, 100 ml of methanol are added to the lemon-yellow suspension, the solid is filtered off with suction, washed three times with about 30 ml of methanol and then dried in vacuo. Yield: 10.4 g (9.5 mmol), 95%; purity: about 99.5% according to NMR.

(180) The following compounds can be prepared analogously:

(181) TABLE-US-00040 Ex. Complex Brominated complex Yield Ir(L42-Br).sub.3 06 Ir(L42).sub.3 07 Ir(L42-Br).sub.3 93% Ir(L95-Br).sub.3 08 Ir(L95).sub.3 09 Ir(L95-Br).sub.3 95% Ir(L102-Br).sub.3 0 Ir(L102).sub.3 Ir(L102-Br).sub.3 92% Ir(L129-Br).sub.3 Ir(L129).sub.3 Ir(L129-Br).sub.3 96% fac-Ir(L78-Br).sub.3 fac-Ir(L78).sub.3 fac-Ir(L78-Br).sub.3 85% Ir500-Br.sub.2 Ir500 Ir500-Br.sub.2 89% Ir505-Br.sub.3 Ir505 Ir505-Br.sub.3 93% Ir506-Br.sub.2 0 Ir506 Ir506-Br.sub.2 92% Ir513-Br Ir513 Ir513-Br 96%
2) Suzuki Coupling on the Iridium Complexes:
Variant a, Two-Phase Reaction Mixture:

(182) 0.6 mmol of tri-o-tolylphosphine and then 0.1 mmol of palladium(II) acetate are added to a suspension of 10 mmol of a brominated complex, 40-80 mmol of the boronic acid or boronic acid ester and 80 mmol of tripotassium phosphate in a mixture of 300 ml of toluene, 100 ml of dioxane and 300 ml of water, 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 separated off, the organic phase is washed three times with 200 ml of water, once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. The solid material is filtered off through a Celite bed and rinsed with toluene, the toluene is removed virtually completely in vacuo, 300 ml of ethanol are added, the precipitated crude product is filtered off with suction, washed three times with 100 ml of EtOH each time and dried in vacuo. The crude product is passed through a silica-gel column with toluene twice. The metal complex is finally heated or sublimed. The heating is carried out in a high vacuum (p about 10.sup.6 mbar) in the temperature range from about 200-300 C. The sublimation is carried out in a high vacuum (p about 10.sup.6 mbar) in the temperature range from about 300-400 C., with the sublimation preferably being carried out in the form of a fractional sublimation.

(183) Variant B, One-Phase Reaction Mixture:

(184) 0.6 mmol of tri-o-tolylphosphine and then 0.1 mmol of palladium(II) acetate are added to a suspension of 10 mmol of a brominated complex, 40-80 mmol of the boronic acid or boronic acid ester and 60-100 mmol of the base (potassium fluoride, tripotassium phosphate, potassium carbonate, caesium carbonate, etc., in each case anhydrous) 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.), and the mixture is heated under reflux for 1-24 h. Alternatively, other phosphines, such as tri-tert-butylphosphine, S-Phos, S-Phos, xantphos, etc., can be employed, where the preferred phosphine:palladium ratio in the case of these phosphines is 2:1 to 1.2:1. The solvent is removed in vacuo, the product is taken up in a suitable solvent (toluene, dichloromethane, ethyl acetate, etc.) and purified as described under Variant A.

Synthesis of Ir588.SUB.3

(185) ##STR00824##
Variant B:

(186) Use of 10.9 g (10.0 mmol) of Ir(L22-Br).sub.3 and 4.9 g (40.0 mmol) of phenylboronic acid [98-80-6], 32.5 g (100 mmol) of caesium carbonate, 62 mg (0.15 mmol) of S-Phos [657408-07-6], 25 mg (0.1 mmol) of palladium(II) acetate, 200 ml of dioxane, 100 C., 8 h. Chromatographic separation on silica gel with toluene/ethyl acetate (90:10, vv). Yield: 6.9 g (6.4 mmol), 64%; purity: about 99.8% according to HPLC.

(187) The following compounds can be prepared analogously:

(188) TABLE-US-00041 Complex Boronic acid Ex. Variant Product Yield Ir589 Ir(L42-Br).sub.3 1233200-59-3 B S-Phos Chromatographic separation using toluene 63% Ir590 Ir(L95-Br).sub.3 1071924-15-6 B S-Phos Chromatographic separation using toluene 55% Ir591 Ir(L102-Br).sub.3 333432-28-3 A Chromatographic separation using DCM 42% Ir592 Ir(L129-Br).sub.3 5122-95-2 A Chromatographic separation using toluene 96% Ir593 Ir500-Br.sub.2 100379-00-8 B S-Phos Chromatographic separation using EA/DCM (95:5 vv) 39% Ir594 Ir513-Br 1251825-65-6 A Chromatographic separation using DCM 0 46%
3) Buchwald Coupling on the Iridium Complexes:

(189) 0.4 mmol of tri-tert-butylphosphine and then 0.3 mmol of palladium(II) acetate are added to a mixture of 10 mmol of the brominated complex, 40 mmol of the diarylamine or carbazole, 45 mmol of sodium tert-butoxide in the case of amines 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, and the mixture is heated under reflux for 16 h with vigorous stirring. After cooling, the aqueous phase is separated off, washed twice with 200 ml of water, once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. The solid material is filtered off through a Celite bed and rinsed with toluene, the solvent is removed virtually completely in vacuo, 300 ml of ethanol are added, the precipitated crude product is filtered off with suction, washed three times with 100 ml of EtOH each time and dried in vacuo. The crude product is purified by chromatography on silica gel with toluene twice. The metal complex is finally heated or sublimed. The heating is carried out in a high vacuum (p about 10.sup.6 mbar) in the temperature range from about 200-300 C. The sublimation is carried out in a high vacuum (p about 10.sup.6 mbar) in the temperature range from about 300-400 C., with the sublimation preferably being carried out in the form of a fractional sublimation.

Synthesis of Ir595

(190) ##STR00831##

(191) Use of 11.8 g (10 mmol) of Ir(L42-Br).sub.3 and 14.5 g (40 mmol) of N-[1,1-biphenyl]-4-yl-9,9-dimethyl-9H-fluoren-2-amine [897671-69-1]. Heating. Yield: 7.9 g (3.9 mmol), 39%; purity: about 99.8% according to HPLC.

(192) The following compounds can be prepared analogously:

(193) TABLE-US-00042 Product Starting material Ex. Amine or carbazole Yield Ir596 Ir(L95-Br).sub.3 [1257220-47-5] 43% Ir597 Ir500-Br.sub.2 [244-78-0] 40%
4) Cyanation of the Iridium Complexes:

(194) 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 200 C. for 20 h. After cooling, the solvent is removed in vacuo, the residue is taken up in 500 ml of dichloromethane, the copper salts are filtered off via Celite, the dichloromethane is evaporated virtually to dryness in vacuo, 100 ml of ethanol are added, the precipitated solid is filtered off with suction, washed twice with 50 ml of ethanol each time and dried in vacuo. Chromatography or hot extraction and fractional sublimation of the crude product as described in 1) variant A.

Synthesis of Ir598

(195) ##STR00834##

(196) Use of 11.8 g (10 mmol) of Ir(L42-Br).sub.3 and 3.5 g (39 mmol) of copper(I) cyanide. Sublimation. Yield: 4.7 g (4.6 mmol), 46%; purity: about 99.8% according to HPLC.

(197) The following compounds can be prepared analogously:

(198) TABLE-US-00043 Ex. Product Yield Ir599 fac-Ir(L78-Br).sub.3 + CuCN > Ir599 39% Ir600 Ir513-Br + CuCN > Ir600 63%
5) Borylation of the Iridium Complexes:

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

Synthesis of Ir(L42-B).SUB.3

(200) ##STR00837##

(201) Use of 11.8 g (10 mmol) of Ir(L42-Br).sub.3 and 9.1 g (36 mmol) of bis(pinacolato)diborane [73183-34-3], DMSO, 120 C., 6 h, taking-up and Celite filtration in THF, recrystallisation from THF:methanol. Yield: 7.5 g (5.7 mmol), 57%; purity: about 99.8% according to HPLC.

(202) The following compounds can be prepared analogously:

(203) TABLE-US-00044 Ex. Starting material Product Yield Ir(L95-B).sub.3 Ir(L95-Br).sub.3 Ir(L95-B).sub.3 55% Ir500-B.sub.2 0 Ir500-Br.sub.2 Ir500-B.sub.2 59% Ir506-B.sub.2 Ir506-Br.sub.2 Ir506-B.sub.2 64%
Polymers Containing the Metal Complexes:
General Polymerisation Procedure for the Bromides or Boronic Acid Derivatives as Polymerisable Group, Suzuki Polymerisation
Variant ATwo-Phase Reaction Mixture:

(204) The monomers (bromides and boronic acids or boronic acid esters, purity according to HPLC>99.8%) in the composition indicated in the table are dissolved or suspended in a mixture of 2 parts by volume of toluene: 6 parts by volume of dioxane: 1 part by volume of water in a total concentration of about 100 mmol/l. 2 mol equivalents of tripotassium phosphate per Br functionality employed are then added, the mixture is stirred for a further 5 min., 0.03 to 0.003 mol equivalent of tri-ortho-tolylphosphine and then 0.005 to 0.0005 mol equivalent of palladium(II) acetate (phosphine to Pd ratio preferably 6:1) per Br functionality employed are then added, and the mixture is heated under reflux for 2-3 h with very vigorous stirring. If the viscosity of the mixture increases excessively, it can be diluted 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, 0.05 mol equivalent per boronic acid functionality employed of a monobromoaromatic compound are added for end capping, and then, 30 min. later, 0.05 mol equivalent per Br functionality employed of a monoboronic acid or a monoboronic acid ester is 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 separated off, the organic phase is washed twice with 300 ml of water each time, dried over magnesium sulfate, filtered through a Celite bed in order to remove palladium and then evaporated to dryness. The crude polymer is dissolved in THF (concentration about 10-30 g/l), and the solution is allowed to run slowly, with very vigorous stirring, into twice the volume of methanol. The polymer is filtered off with suction and washed three times with methanol.

(205) The reprecipitation process is repeated three times, the polymer is then dried to constant weight at 30-50 C. in vacuo.

(206) Variant BOne-Phase Reaction Mixture:

(207) The monomers (bromides and boronic acids or boronic acid esters, purity according to HPLC>99.8%) in the composition indicated in the table are dissolved or suspended in a solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.) in a total concentration of about 100 mmol/l. 3 mol equivalents of base (potassium fluoride, tripotassium phosphate, potassium carbonate, caesium carbonate, etc., in each case anhydrous) per Br functionality are then added, and the weight equivalent of glass beads (diameter 3 mm) is added, the mixture is stirred for a further 5 min., 0.03 to 0.003 mol equivalent of tri-ortho-tolylphosphine and then 0.005 to 0.0005 mol equivalent of palladium(II) acetate (phosphine to Pd ratio preferably 6:1) per Br functionality are then added, and the mixture is then heated under reflux for 2-3 h with very vigorous stirring. Alternatively, other phosphines, such as tri-tert-butylphosphine, S-Phos, X-Phos, xantphos, etc., can be employed, where the preferred phosphine:palladium ratio in the case of these phosphines is 2:1 to 1.3:1. After a total reaction time of 4-12 h, 0.05 mol equivalent of a monobromoaromatic compound and then, 30 min. later, 0.05 mol equivalent of a monoboronic acid or a monoboronic acid ester is added for end capping, and the mixture is boiled for a further 1 h. The solvent is substantially removed in vacuo, the residue is taken up in toluene, and the polymer is purified as described under variant A.

(208) Monomers/End Cappers:

(209) ##STR00844## ##STR00845##
Polymers:

(210) Composition of the polymers, mol %:

(211) TABLE-US-00045 M3 M4 Ir complex/ Polymer M1 [%] M2 [%] [%] [%] [%] P1 30 45 Ir(L95-Br).sub.3/10 P2 10 10 35 Ir505-Br.sub.3/10 P3 30 40 Ir500-Br.sub.2/10 P4 10 30 10 20 Ir506-B.sub.2 /10

(212) Molecular weights and yield of the polymers according to the invention:

(213) TABLE-US-00046 Polymer Mn [gmol.sup.-1] Polydispersity Yield P1 147,000 4.6 60% P2 158,000 5.1 57% P3 239,000 2.4 63% P4 235,000 2.3 67%

Example

Comparison of the Photoluminescence Spectra

(214) The FIGURE shows the photoluminescence spectrum of complex Ir(L3).sub.3, i.e. a tris(phenylisoquinoline)iridium complex which contains a group of the formula (3), compared with the spectrum of the corresponding complex without the group of the formula (3). The spectra were measured in an approx. 10.sup.5 molar solution in degassed toluene at room temperature. The narrower emission band having a full width at half maximum (FWHM) value of 48 nm compared with 74 nm in the case of the compound without a group of the formula (3) is clearly evident. The complex according to the invention furthermore has higher photoluminescence quantum efficiency.

Example

Production of OLEDs

(215) 1) Vacuum-Processed Devices:

(216) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 2004/058911, which is adapted to the circumstances described here (layer-thickness variation, materials used).

(217) The results for various OLEDs are presented in the following examples. Glass plates with structured ITO (50 nm, indium tin oxide) form the substrates to which the OLEDs are applied. The OLEDs have in principle the following layer structure: substrate/hole-transport layer 1 (HTL1) consisting of HTM doped with 3% of NDP-9 (commercially available from Novaled), 20 nm/hole-transport layer 2 (HTL2)/optional electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm

(218) Firstly, vacuum-processed OLEDs are described. For this purpose, all materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or matrix materials in a certain proportion by volume by coevaporation. An expression such as M3:M2:Ir(L1).sub.3 (55%:35%:10%) here means that material M3 is present in the layer in a proportion by volume of 55%, M2 is present in the layer in a proportion of 35% and Ir(L1).sub.3 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials. The precise structure of the OLEDs is shown in Table 1. The materials used for the production of the OLEDs are shown in Table 7.

(219) The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A) and the voltage (measured at 1000 cd/m.sup.2 in V) are determined from current/voltage/luminance characteristic lines (IUL characteristic lines). For selected experiments, the lifetime is determined. The lifetime is defined as the time after which the luminous density has dropped to a certain proportion from a certain initial luminous density. The expression LT50 means that the lifetime given is the time at which the luminous density has dropped to 50% of the initial luminous density, i.e. from, for example, 1000 cd/m.sup.2 to 500 cd/m.sup.2. Depending on the emission colour, different initial luminances were selected. The values for the lifetime can be converted to a figure for other initial luminous densities with the aid of conversion formulae known to the person skilled in the art. The lifetime for an initial luminous density of 1000 cd/m.sup.2 is a usual figure here.

(220) Use of Compounds According to the Invention as Emitter Materials in Phosphorescent OLEDs

(221) The compounds according to the invention can be employed, inter alia, as phosphorescent emitter materials in the emission layer in OLEDs. The iridium compounds shown in Table 7 are used as comparison in accordance with the prior art. The results for the OLEDs are summarised in Table 2.

(222) TABLE-US-00047 TABLE 1 Structure of the OLEDs HTL2 EBL HBL Thick- Thick- EML Thick- ETL Ex. ness ness Thickness ness Thickness Red OLEDs D-IrR1 HTM M7:M8:Ir-R1 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-Ir(L3).sub.3 HTM M7:M8:Ir(L3).sub.3 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-Ir(L4)).sub.3 HTM M7:M8:Ir(L4).sub.3 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-Ir(L95).sub.3 HTM M7:M8:Ir(L95).sub.3 ETM1: 280 nm (55%:40%:5%) ETM2 35 nm (50%:50%) 40 nm D-Ir(L101).sub.3 HTM M7:M8:Ir(L101).sub.3 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-Ir548 HTM M7:M8:Ir548 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-Ir555 HTM M6:M8:Ir555 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-Ir587 HTM M6:M8:Ir587 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-IrR2 HTM M9:Ir-R2 ETM1: 280 nm (92%:8%) ETM2 35 nm (50%:50%) 40 nm D-Ir543 HTM M9:Ir543 ETM1: 280 nm (92%:8%) ETM2 35 nm (50%:50%) 40 nm D-Ir544 HTM M9:Ir544 ETM1: 280 nm (92%:8%) ETM2 35 nm (50%:50%) 40 nm D-Ir556 HTM M9:Ir556 ETM1: 280 nm (95%:5%) ETM2 35 nm (50%:50%) 40 nm D-Ir557 HTM M9:Ir557 ETM1: 280 nm (92%:8%) ETM2 35 nm (50%:50%) 40 nm D-Ir568 HTM M9:Ir568 ETM1: 280 nm (95%:5%) ETM2 35 nm (50%:50%) 40 nm D-Ir583 HTM M9:Ir583 ETM1: 280 nm (92%:8%) ETM2 35 nm (50%:50%) 40 nm D-IrR3 HTM M7:M8:Ir-R3 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-Ir545 HTM M7:M8:Ir545 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-IrR4 HTM M7:M8:Ir-R4 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-Ir546 HTM M7:M8:Ir546 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-Pt-R1 HTM M7:M8:Pt-R1 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-Pt003 HTM M7:M8:Pt003 ETM1: 280 nm (65%:30%:5%) ETM2 35 nm (50%:50%) 40 nm D-Ir(L129).sub.3 HTM M7:M8: D- ETM1: 280 nm Ir(L129).sub.3 ETM2 (60%:30%:10%) (50%:50%) 35 nm 40 nm D-Ir(L132).sub.3 HTM M7:M8: D- ETM1: 280 nm Ir(L132).sub.3 ETM2 (60%:30%:10%) (50%:50%) 35 nm 40 nm D-Ir552 HTM M6:M8: D-Ir552 ETM1: 280 nm (50%:45%:5%) ETM2 35 nm (50%:50%) 40 nm Yellow OLEDs D-Ir-Y1 HTM M7:M8:Ir-Y1 ETM1: 230 nm (62%:30%:8%) ETM2 25 nm (50%:50%) 45 nm D-Ir(L28).sub.3 HTM M7:M8:Ir(L28).sub.3 ETM1: 230 nm (62%:30%:8%) ETM2 25 nm (50%:50%) 45 nm D-Ir-Y2 HTM M7:M8:Ir-Y2 ETM1: 230 nm (62%:30%:8%) ETM2 25 nm (50%:50%) 45 nm D-Ir501 HTM M7:M8:Ir-501 ETM1: 230 nm (62%:30%:8%) ETM2 25 nm (50%:50%) 45 nm Green OLEDs D-Ir-G1 HTM M7:M8:Ir-G1 HBM2 ETM1: 230 nm (65%:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Ir(L1).sub.3 HTM M7:M8:Ir(L1).sub.3 HBM2 ETM1: 230 nm (65%:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Ir(L22).sub.3 HTM M7:M8:Ir(L22).sub.3 HBM2 ETM1: 230 nm (65%:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Ir(L33).sub.3 HTM M7:M8:Ir(L33).sub.3 HBM2 ETM1: 230 nm (65%:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Ir(L34).sub.3 HTM M7:M8:Ir(L34).sub.3 HBM2 ETM1: 230 nm (65%:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Ir(L35).sub.3 HTM M7:M8:Ir(L35).sub.3 HBM2 ETM1: 230 nm (65%:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Ir(L38).sub.3 HTM M7:M8:Ir(L38).sub.3 HBM2 ETM1: 230 nm (65%:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Ir(L42).sub.3 HTM M7:M8:Ir(L42).sub.3 HBM2 ETM1: 230 nm (65%:30% :5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Ir(L48).sub.3 HTM M7:M8:Ir(L48).sub.3 HBM2 ETM1: 230 nm (65%:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Ir(L49).sub.3 HTM M7:M8:Ir(L49).sub.3 HBM2 ETM1: 230 nm (65%:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Ir(L50).sub.3 HTM M7:M8:Ir(L50).sub.3 HBM2 ETM1: 230 nm (65:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Ir(L52).sub.3 HTM M7:M8:Ir(L52).sub.3 HBM2 ETM1: 230 nm 25 nm 10 nm ETM2 (50%:50%) 35 nm D-Ir-G2 HTM M7:M8:Ir-G2 HBM2 ETM1: 230 nm (65%:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Ir(L8).sub.3 HTM M7:M8:Ir(L8).sub.3 HBM2 ETM1: 230 nm (65%:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Pt(L139) HTM M7:M8:Pt(L139) HBM2 ETM1: 230 nm (65%:33%:8%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Pt(L143) HTM M7:M8:Pt(L143) HBM2 ETM1: 230 nm (65%:30%:5%) 10 nm ETM2 25 nm (50%:50%) 35 nm D-Pt(L146) HTM M7:M8:Pt(L146) HBM2 ETM1: 230 nm (60%:30%:10%) 10 nm ETM2 25 nm (50%:50%) 35 nm Blue OLEDs D-Ir-B1 HTM EBM M1:M4:Ir-B1 HBM1 ETM1: 190 nm 10 nm (60%:35%:5%) 10 nm ETM2 25 nm (50%:50%) 15 nm D-Ir(L74).sub.3 HTM EBM M1:M4:Ir(L74).sub.3 HBM1 ETM1: 190 nm 10 nm (60%:35%:5%) 10 nm ETM2 25 nm (50%:50%) 15 nm D-Ir(L77).sub.3 HTM EBM M1:M4:Ir(L77).sub.3 HBM1 ETM1: 190 nm 10 nm (60%:35%:5%) 10 nm ETM2 25 nm (50%:50%) 15 nm D-Ir-B2 HTM EBM M10:M4:Ir-B2 HBM1 ETM1: 190 nm 10 nm (65%:25%:10%) 10 nm ETM2 25 nm (50%:50%) 15 nm D-fac- HTM EBM M10:M4:fac- HBM1 ETM1: Ir(L78).sub.3 190 nm 10 nm Ir(L78).sub.3 10 nm ETM2 (65%:25%:10%) (50%:50%) 25 nm 15 nm D-fac- HTM EBM M10:M4:fac- HBM1 ETM1: Ir(L486).sub.3 190 nm 10 nm Ir(L86).sub.3 10 nm ETM2 (65%:25%:10%) (50%:50%) 25 nm 15 nm D-fac- HTM EBM M10:M4:fac- HBM1 ETM1: Ir(L87).sub.3 190 nm 10 nm Ir(L87).sub.3 10 nm ETM2 (65%:25%:10%) (50%:50%) 25 nm 15 nm D-fac- HTM EBM M10:M4:fac- HBM1 ETM1: Ir(L88).sub.3 190 nm 10 nm Ir(L88).sub.3 10 nm ETM2 (65%:25%:10%) (50%:50%) 25 nm 15 nm D-fac- HTM EBM M10:M4:fac- HBM1 ETM1: Ir(89).sub.3 190 nm 10 nm Ir(L89).sub.3 10 nm ETM2 (65%:25%:10%) (50%:50%) 25 nm 15 nm D-Pt(L148) HTM EBM M10:M4 Pt(L148) HBM1 ETM1: 190 nm 10 nm (60%:30%:10%) 10 nm ETM2 25 nm (50%:50%) 15 nm D-Pt(L150) HTM EBM M10:M4:Pt(L150) HBM1 ETM1: 190 nm 10 nm 65%:25%:10%) 10 nm ETM2 25 nm (50%:50%) 15 nm D-Pt(L152) HTM EBM M10:M4:Pt(L152) HBM1 ETM1: 190 nm 10 nm (60%:35%:5%) 10 nm ETM2 25 nm (50%:50%) 15 nm

(223) TABLE-US-00048 TABLE 2 Results of vacuum-processed OLEDs EQE (%) Voltage (V) CIE x/y LT80 (h) Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Red OLEDs D-IrR1 13.3 2.9 0.67/0.33 14000 D-Ir(L3).sub.3 15.5 3.0 0.68/0.32 18000 D-Ir(L4)).sub.3 16.9 3.0 0.68/0.32 26000 D-Ir(L95).sub.3 17.4 3.2 0.68/0.32 15000 D-Ir(101).sub.3 17.9 3.1 0.68/0.32 16000 D-Ir548 17.0 3.0 0.67/0.32 14500 D-Ir555 18.7 3.0 0.67/0.32 13000 D-Ir587 19.3 3.2 0.68/0.32 17000 D-IrR2 18.9 3.8 0.66/0.34 30000 D-Ir543 19.6 3.6 0.66/0.34 39000 D-Ir544 22.4 3.6 0.65/0.34 54000 D-Ir556 19.6 3.4 0.66/0.34 36000 D-Ir557 19.2 3.3 0.67/0.33 40000 D-Ir568 19.4 3.5 0.63/0.36 47000 D-Ir583 19.0 3.3 0.67/0.33 42000 D-IrR3 16.3 3.2 0.62/0.37 21000 D-Ir542 21.0 3.2 0.64/0.35 33000 D-IrR4 12.7 3.3 0.70/0.29 17000 D-Ir546 18.0 3.2 0.71/0.28 39000 D-Pt-R1 11.0 3.4 0.68/0.32 11000 D-Pt003 15.8 3.4 0.69/0.31 16000 D-Ir(L129).sub.3 19.4 3.2 0.66/0.33 17000 D-Ir(L132).sub.3 17.9 3.2 0.67/0.32 15000 D-Ir552 18.7 3.1 0.66/0.34 17500 Yellow OLEDs D-Ir-Y1 19.8 3.0 0.38/0.61 32000 D-Ir(L28).sub.3 22.3 3.1 0.40/0.59 39000 D-Ir-Y2 21.5 2.8 0.46/0.53 41000 D-Ir501 23.8 2.9 0.48/0.52 49000 Green OLEDs D-Ir-G1 18.0 3.4 0.32/0.64 8000 D-Ir(L1).sub.3 20.4 3.3 0.34/0.61 22000 D-Ir(L22).sub.3 21.3 3.3 0.28/0.62 23000 D-Ir(L33).sub.3 22.4 3.4 0.31/0.63 21000 D-Ir(L34).sub.3 22.6 3.4 0.31/0.63 25000 D-Ir(L35).sub.3 22.4 3.4 0.31/0.63 24000 D-Ir(L38).sub.3 21.4 3.3 0.30/0.64 19000 D-Ir(L42).sub.3 22.7 3.3 0.29/0.62 26000 D-Ir(L48).sub.3 22.4 3.4 0.31/0.63 26000 D-Ir(L49).sub.3 22.3 3.4 0.31/0.63 22000 D-Ir(L50).sub.3 22.3 3.3 0.31/0.64 23000 D-Ir(L52).sub.3 23.2 3.4 0.31/0.64 24000 D-Ir-G2 19.1 3.2 0.35/0.61 19000 D-Ir(L8).sub.3 22.1 3.3 0.36/0.62 19000 D-Pt(L139) 21.8 3.5 0.33/0.63 17000 D-Pt(L143) 22.0 3.6 0.34/0.62 18000 D-Pt(L146) 22.4 3.6 0.33/0.61 20500 Blue OLEDs LT50 (h) 1000 cd/m.sup.2 D-Ir-B1 16.3 4.8 0.18/0.37 1000 D-Ir(L74).sub.3 22.5 4.7 0.16/0.38 1200 D-Ir(L77).sub.3 21.0 4.8 0.15/0.36 700 D-Ir-B2 3.2 5.3 0.16/0.06 50 D-fac-Ir(L78).sub.3 6.4 5.2 0.16/0.09 150 D-fac-Ir(L86).sub.3 8.4 5.5 0.16/0.11 200 D-fac-Ir(L87).sub.3 9.3 5.6 0.15/0.10 D-fac-Ir(L88).sub.3 8.8 5.6 0.16/0.10 200 D-fac-Ir(89).sub.3 6.7 6.0 0.15/0.08 D-Pt(L148) 15.4 5.4 0.15/0.19 800 D-Pt(L150) 17.7 5.2 0.15/0.23 1600 D-Pt(L152) 16.0 5.4 0.15/0.19 1100
2) Solution-Processed Devices:
A: From Soluble Functional Materials

(224) The iridium complexes according to the invention can also be processed from solution, where they result in OLEDs which are significantly simpler as far as the process is concerned, compared with the vacuum-processed OLEDs, with nevertheless good properties. The production of components of this type 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 20041037887). The structure is composed of substrate/ITO/PEDOT (80 nm)/interlayer (80 nm)/emission layer (80 nm)/cathode. To this end, use is made of substrates from Technoprint (soda-lime glass), to which the ITO structure (indium tin oxide, a transparent, conductive anode) is applied. The substrates are cleaned with DI water and a detergent (Deconex 15 PF) in a clean room and then activated by a UV/ozone plasma treatment. An 80 nm layer of PEDOT (PEDOT is a polythiophene derivative (Baytron P VAI 4083sp.) from H. C. Starck, Goslar, which is supplied as an aqueous dispersion) is then applied as buffer layer by spin coating, likewise in the clean room. The spin rate required depends on the degree of dilution and the specific spin coater geometry (typically for 80 nm: 4500 rpm). In order to remove residual water from the layer, the substrates are dried by heating on a hotplate at 180 C. for 10 minutes. The interlayer used serves for hole injection, in this case HIL-012 from Merck is used. The interlayer may alternatively also be replaced by one or more layers, which merely have to satisfy the condition of not being detached again by the subsequent processing step of EML deposition from solution. In order to produce the emission layer, the emitters according to the invention are dissolved in toluene together with the matrix materials. The typical solids content of such solutions is between 16 and 25 g/l if, as here, the typical layer thickness of 80 nm for a device is to be achieved by means of spin coating. The solution-processed devices comprise an emission layer comprising (polystyrene):M5:M6:Ir(L).sub.3 (25%:25%:40%:10%). The emission layer is applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 130 C. for 30 min. Finally, a cathode is applied by vapour deposition from barium (5 nm) and then aluminium (100 nm) (high-purity metals from Aldrich, particularly barium 99.99% (Order No. 474711); vapour-deposition equipment from Lesker, inter alia, typical vapour-deposition pressure 510.sup.6 mbar). Optionally, firstly a hole-blocking layer and then an electron-transport layer and only then the cathode (for example Al or LiF/Al) can be applied by vacuum vapour deposition. In order to protect the device against air and atmospheric moisture, the device is finally encapsulated and then characterised. The OLED examples given have not yet been optimised, Table 3 summarises the data obtained.

(225) TABLE-US-00049 TABLE 3 Results with solution-processed materials EQE (%) Voltage (V) CIE x/y Ex. Emitter 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Red OLEDs Sol-D-Ir-R2 Ir-R2 17.1 3.9 0.66/0.34 Sol-D-Ir543 Ir543 19.7 3.9 0.66/0.34 Sol-D-Ir544 Ir544 21.2 3.8 0.65/0.34 Sol-D-Ir(L95).sub.3 Ir(L95).sub.3 17.2 3.7 0.67/0.32 Sol-D-Ir564 Ir564 18.7 3.6 0.68/0.31 Sol-D-Ir567 Ir567 18.5 3.2 0.68/0.31 Yellow OLEDs Sol-D-Ir-Y3 IrY3 19.5 3.9 0.48/0.49 Sol-D-Ir(L2).sub.3 Ir(L2).sub.3 22.1 4.0 0.49/0.50 Sol-D-Ir(L12).sub.3 Ir(L12).sub.3 21.3 4.1 0.50/0.47 Green OLEDs Sol-D-Ir-G3 Ir-G3 18.5 4.3 0.34/0.61 Sol-D-Ir(L26).sub.3 Ir(L26).sub.3 21.7 4.4 0.34/0.61 Sol-D-Ir589 Ir589 21.0 4.2 0.36/0.60 Sol-D-Ir593 Ir593 21.7 4.2 0.33/0.65 Sol-D-Pt(L146) Pt(L146) 21.4 4.3 0.33/0.61
B: From Polymeric Functional Materials:

(226) Production of the OLEDs as described under A: For the production of the emission layer, the polymers according to the invention are dissolved in toluene. The typical solids content of such solutions is between 10 and 15 g/l if, as here, the typical layer thickness of 80 nm for a device is to be achieved by means of spin coating. The said OLED examples have not yet been optimised, Table 4 summarises the data obtained.

(227) TABLE-US-00050 TABLE 4 Results with solution-processed materials EQE (%) Voltage (V) CIE x/y Ex. Polymer 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Red OLEDs D-P1 P1 16.6 3.7 0.68/0.32 Green OLEDs D-P2 P2 17.5 4.2 0.34/0.61 D-P3 P3 18.1 4.2 0.33/0.63 D-P4 P4 18.6 4.3 0.33/0.62
1) White-Emitting OLEDs

(228) A white-emitting OLED having the following layer structure is produced in accordance with the general processes from 1):

(229) TABLE-US-00051 TABLE 5 Structure of the white OLEDs EML EML EML HTL2 Red Blue Green HBL ETL Thick- Thick- Thick- Thick- Thick- Thick- Ex. ness ness ness ness ness ness D-W1 HTM EBM: M1:M3: M3: M3 ETM1: 230 nm IrL544 IrL536 Ir(L42).sub.3 10 nm ETM2 (97%:3%) (45%: (90%:10%) (50%:50%) 9 nm 50%:5%) 7 nm 30 nm 8 nm

(230) TABLE-US-00052 TABLE 6 Device results EQE (%) Voltage (V) CIE x/y LT50 (h) Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 D-W1 22.4 6.1 0.42/0.39 6000

(231) TABLE-US-00053 TABLE 7 Structural formulae of the materials used HTM EBM = M10 M1 M2 0 M3 = HBM2 M4 = HBM1 M5 M6 M7 M8 148896-39-3 M9 435293-93-9 Ir-R1 1056874-46-4 Ir-R2 1361033-48-8 Ir-R3 0 848127-98-0 Ir-R4 890307-63-8 Pt-R1 458532-65-5 Ir-Y1 1215281-24-5 Ir-Y2 459133-57-4 Ir-Y3 693794-98-8 Ir-G1 359014-71-4 Ir-G2 856219-87-9 Ir-G3 1013022-35-9 Ir-B1 869486-05-5 Ir-B2 0 ETM1 ETM2

Example L160

1-Phenyl-1H-1,2,3,4-tetrahydro-1,4-methanobenz[f]-indazole

(232) ##STR00872##

(233) Procedure analogous to H. K. Lee et al., Synth. Commun., 2013, 43, 915. A mixture of 25.1 g (100 mmol) of S53, 11.9 g (110 mmol) of phenylhydrazine [100-63-0], 19.2 g (200 mmol) of sodium tert-butoxide, 636 mg (10 mmol) of copper bronze and 500 ml of PEG-400 is stirred on a water separator at 120 C. for 10 h. After cooling, 1000 ml of ethyl acetate are added, the solid material is filtered off with suction via a Celite bed, the filtrate is washed five times with 300 ml of water each time, and once with 500 ml of saturated sodium chloride solution, and the organic phase is dried over magnesium sulfate. After removal of the solvent, the residue is recrystallised three times from DMF/EtOH, and the residue is subjected to fractional bulb-tube distillation (T about 150 C., p about 10.sup.4 mbar). Yield: 12.5 g (48 mmol), 48%; purity: about 99.5% according to .sup.1H-NMR.

(234) The following compounds can be prepared analogously:

(235) TABLE-US-00054 Ex. Starting materials Product Yield L161 S54 51% L162 1194655-78-1 26%

Preparation of Fac-Tris-Homoleptic Iridium Complexes

(236) The preparation is carried out analogously to 1) Homoleptic tris-facial iridium complexes of the phenylpyridine, phenylimidazole or phenylbenzimidazole type.

(237) TABLE-US-00055 Variant Reaction medium Reaction temp. Reaction time Ligand Ir complex Suspension medium Ex. L Diastereomer Extractant Yield Ir(L160).sub.3 L160 ,-C3 A 260 C. 60 h Ethyl acetate o-Xylene 23% Ir(L161).sub.3 L161 Ir(L161).sub.3 as Ir(L160).sub.3 33% Ir(L162).sub.3 L162 ,-C3 A 260 C. 40 h Ethanol o-Xylene 22%

OLED Examples

(238) The OLEDs are produced by vacuum processing, as described above.

(239) Structure of the OLEDs:

(240) TABLE-US-00056 HTL2 EBL EML HBL ETL Ex. Thickness Thickness Thickness Thickness Thickness D-fac- HTM EBM M10:M4:fac- HBM1 ETM1: Ir(161).sub.3 190 nm 10 nm Ir(L161).sub.3 10 nm ETM2 (65%:30%:5%) (50%:50%) 25 nm 15 nm D-fac- HTM EBM M10:M4:fac- HBM1 ETM1: Ir(162).sub.3 190 nm 10 nm Ir(L162).sub.3 10 nm ETM2 (60%:35%:5%) (50%:50%) 25 nm 15 nm
Device Results:

(241) TABLE-US-00057 EQE (%) Voltage (V) CIE x/y Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 D-fac-Ir(161).sub.3 14.2 4.8 0.19/0.48 D-fac-Ir(162).sub.3 6.5 5.0 0.14/0.12