Metal complexes

Abstract

The present invention relates to metal complexes 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) comprising a moiety M(L).sub.n of formulae (2), (3), or (4): ##STR01335## wherein: M is a transition metal; X is selected, on each occurrence, identically or differently, from the group consisting of CR and N; 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 are optionally substituted by one or more radicals R.sup.1, and wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR.sup.1, and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.1, or 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 arylheteroarylamino 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 define 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 are optionally substituted by one or more radicals R.sup.2, and wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S, or CONR.sup.2, and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, or 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 define 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 define a mono- or polycyclic, aliphatic ring system with one another; L′ is, identically or differently on each occurrence, any desired co-ligand; n is 1, 2, or 3; m is 0, 1, 2, 3, or 4; 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 two adjacent groups X are CR and the respective radicals R, together with the C atoms, form a ring of formula (5) or (6); ##STR01336## wherein R.sup.1 and R.sup.2 are as defined above; the dashed bonds indicate the linking of the two carbon atoms in the ligand; A.sup.1 and A.sup.3 are, identically or differently, on each occurrence, C(R.sup.3).sub.2, O, S, NR.sup.3, or C(═O); A.sup.2 is C(R.sup.1).sub.2, O, S, NR.sup.3, or C(═O); G is an alkylene group having 1, 2, or 3 C atoms optionally substituted by one or more radicals R.sup.2, or is —CR.sup.2═CR.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, F, 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 optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S, or CONR.sup.2 and wherein one or more H atoms are optionally replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, or 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; and wherein two radicals R.sup.3 bonded to the same carbon atom optionally define an aliphatic or aromatic ring system with one another and thus form a spiro system; and wherein R.sup.3 optionally defines an aliphatic ring system with an adjacent radical R or R.sup.1; and with the proviso that two heteroatoms are not bonded directly to one another in A.sup.1-A.sup.2-A.sup.3.

2. The compound of claim 1, wherein M is selected from the group consisting of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold.

3. The compound of claim 1, wherein M is selected from the group consisting of molybdenum, tungsten, rhenium, ruthenium, osmium, iridium, copper, platinum, and gold.

4. The compound of claim 1, wherein the moiety of formula (2) is selected from the group consisting of formulae (2-A) to (2-Q), the moiety of formula (3) is selected from the group consisting of formulae (3-A) to (3-F), the moiety of formula (4) is selected from the group consisting of formulae (4-A) to (4-F): ##STR01337## ##STR01338## ##STR01339## ##STR01340## ##STR01341## ##STR01342## ##STR01343##

5. The compound of claim 1, wherein the moiety of formula (2) is selected from the group consisting of formulae (2-1) to (2-5), the moiety of formula (3) is selected from the group consisting of formulae (3-1) to (3-3), and the moiety of formula (4) is selected from the group consisting of formulae (4-1) to (4-4): ##STR01344## ##STR01345## ##STR01346## wherein * in each case denotes the positions which are CR, wherein the respective radicals R, together with the C atoms to which they are bonded, define a ring of formula (5) or (6).

6. The compound of claim 1, wherein the structure of formula (5) is selected from the group consisting of formulae (5-A), (5-B), (5-C), and (5-D) and the structure of formula (6) is selected from the group consisting of formulae (6-A), (6-B), and (6-C): ##STR01347## wherein A.sup.1, A.sup.2, and A.sup.3 are, identically or differently on each occurrence, O or NR.sup.3.

7. The compound of claim 1, wherein G is an ethylene group optionally substituted by one or more radicals R.sup.2.

8. The compound of claim 7, wherein R.sup.2 is, identically or differently on each occurrence, an alkyl group having 1 to 4 C atoms or an ortho-arylene group having 6 to 10 C atoms optionally substituted by one or more radicals R.sup.2.

9. The compound of claim 1, wherein, if one or more groups X is nitrogen, a group R selected from the group consisting of CF.sub.3, OCF.sub.3, an alkyl or alkoxy group having 1 to 10 C atoms, an aromatic ring system, a heteroaromatic ring system, an aralkyl group, and a heteroaralkyl group, is bonded as a substituent adjacent to said nitrogen, or R defines a ring of formulae (5) or (6) with an adjacent group R.

10. The compound of claim 1, wherein R, which is bonded in the ortho-position to the metal coordination, is a group selected from the group consisting of aryl groups heteroaryl groups, aryl cyanides, alkyl cyanides, aryl isocyanides, alkyl isocyanides, amines, amides, alcohols, alcoholates, thioalcohols, thioalcoholates, phosphines, phosphites, carbonyl functions, carboxylates, carbamides, or arylacetylides, and alkylacetylides, which are likewise coordinated to the metal M.

11. The compound of claim 1, wherein said compound is selected from the structures of formulae (13) to (18): ##STR01348## ##STR01349## wherein V is a single bond, a bridging unit containing 1 to 80 atoms from the third, fourth, fifth, and/or sixth main group (i.e., group 13, 14, 15, or 16 in accordance with IUPAC), or a 3- to 6-membered homo- or heterocycle and the part-ligands L are covalently bonded to one another or L is covalently bonded to L′.

12. The compound of claim 1, wherein L′ is selected from the group consisting of carbon monoxide, nitrogen monoxide, alkyl cyanides, aryl cyanides, alkyl isocyanides, aryl isocyanides, amines, phosphines, phosphites, arsines, stibines, nitrogen-containing heterocycles, carbenes, hydride, deuteride, F.sup.−, Cl.sup.−, Br.sup.−, I.sup.−, alkylacetylides, arylacetylides, cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic alcoholates, aromatic alcoholates, aliphatic thioalcoholates, aromatic thioalcoholates, amides, carboxylates, aryl groups, O.sup.2−, S.sup.2−, carbides which result in coordination in the form R—C≡M, nitrenes which result in coordination in the form R—N=M, where R generally stands for a substituent, N.sup.3−, diamines, imines, diimines, heterocycles containing two nitrogen atoms, diphosphines, 1,3-diketonates derived from 1,3-diketones, 3-ketonates derived from 3-ketoesters, carboxylates derived from aminocarboxylic acids, salicyliminates derived from salicylimines, dialcoholates, dithiolates, 3-(2-pyridyl)diazoles, 3-(2-pyridyl)triazoles, borates of nitrogen-containing heterocycles and bidentate monoanionic ligands L′, bidentate neutral ligands L′ and bidentate dianionic ligands L′ which, with the metal, define a cyclometallated five-membered ring or six-membered ring having at least one metal-carbon bond.

13. A process for preparing a compound of claim 1 comprising reacting a corresponding free ligand with a metal alkoxide of formula (71), a metal ketoketonate of formula (72), a metal halide of formula (73), a dimeric metal complex of formula (74), or a metal complex of formula (75): ##STR01350## wherein Hal is F, Cl, Br or I, L″ is an alcohol or a nitrile, and (anion) is a non-coordinating anion, and wherein metal compounds which carry both alcoholate and/or halide and/or hydroxyl and also ketoketonate radicals are optionally employed.

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

15. A formulation comprising an oligomer, polymer, or dendrimer of claim 14 and at least one further compound.

16. An electronic device comprising one or more oligomers, polymers, or dendrimers of claim 14.

17. The electronic device of claim 16, wherein said 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.

18. The electronic device of claim 17, comprising an emitting layer comprising a matrix material selected from the group consisting of ketones, phosphine oxides, sulfoxides, sulfones, triarylamines, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazoles, bipolar matrix materials, silanes, azaboroles, boronic esters, diazasilole derivatives, diazaphosphole derivatives, triazine derivatives, zinc complexes, dibenzofuran derivatives, bridged carbazole derivatives, and mixtures thereof.

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

20. An electronic device comprising one or more compounds of claim 1.

21. The electronic device of claim 20, wherein said 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.

22. The electronic device of claim 21, comprising an emitting layer comprising a matrix material selected from the group consisting of ketones, phosphine oxides, sulfoxides, sulfones, triarylamines, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazoles, bipolar matrix materials, silanes, azaboroles, boronic esters, diazasilole derivatives, diazaphosphole derivatives, triazine derivatives, zinc complexes, dibenzofuran derivatives, bridged carbazole derivatives, and mixtures thereof.

23. An organic electroluminescent device comprising a compound of claim 1 employed as an emitting compound in one or more emitting layers.

Description

EXAMPLES

(1) 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.

(2) A: Synthesis of the Synthones S:

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

(3) ##STR00058##

(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 org. 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 sat. 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 can be prepared analogously:

(7) TABLE-US-00001 Ex. Starting materials Product Yield S2 0 68% S3 49%

Example S4: 6-Bromo-1,1,3,3-tetramethylindan-5-ylamine, S4

(8) ##STR00063##

(9) 6.23 g (10 mmol) of rac-BINAP and then 2.24 g (10 mmol) of palladium(II) acetate are added to a mixture of 166.0 g (500 mmol) of 5,6-dibromo-1,1,3,3-tetramethylindane S16a, 83.9 ml (500 mmol) of benzhydrylidenamine [1013-88-3], 52.9 g (550 mmol) of sodium tert-butoxide and 500 ml of toluene, and the mixture is subsequently heated under reflux for 16 h. After cooling, 500 ml of water are added, the org. phase is separated off, washed twice with 500 ml of sat. sodium chloride solution each time, the toluene is removed in a rotary evaporator, the residue is taken up in 1000 ml of THF, 250 ml of 2 N hydrochloric acid are added, and the reaction mixture is heated under reflux for 16 h. The solvent is removed in vacuo, the residue is taken up in 1000 ml of ethyl acetate, the org. phase is washed with sat. sodium hydrogencarbonate solution until pH=7 has been reached, the org. phase is dried over magnesium sulfate, the desiccant is filtered off, 500 g of silica gel are added to the filtrate, and the solvent is removed in vacuo. The loaded silica gel is placed on a silica-gel column (1500 g, slurried in n-heptane:ethyl acetate, 95:5 vv), firstly the benzophenone is eluted with n-heptane:ethyl acetate (95:5 vv), the eluent is then switched to ethyl acetate, and the product is eluted. Yield: 85.8 g (320 mmol), 64%; purity: about 95% according to .sup.1H-NMR.

(10) The following compounds can be prepared analogously:

(11) TABLE-US-00002 Ex. Starting material Product Yield S5  58% S6  67% S7  66% S8  0 65% S9  59% S10 61% S11 63% S12 58% S13 0 55% S14 36% S15 71%

Example S16: 1,1,3,3-Tetramethylindane-5,6-diamine, [83721-95-3], S16

(12) ##STR00086##
Variant A:
A: 5,6-Dibromo-1,1,3,3-tetramethylindane, S16a

(13) ##STR00087##

(14) 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 87.2 g (500 mmol) of 1,1,3,3-tetramethylindane [4834-33-7] in 2000 ml of dichloromethane at such a rate that the temperature does not exceed 25° C., if necessary with countercooling using a cold-water bath. The reaction mixture is stirred at room temperature for a further 16 h, 500 ml of sat. sodium sulfite solution are then added slowly, 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: 121.2 g (365 mmol), 73%; purity: about 95% according to .sup.1H-NMR.

(15) B: 1,1,3,3-Tetramethylindane-5,6-diamine, S16

(16) 9.34 g (15 mmol) of rac-BINAP and then 3.36 g (15 mmol) of palladium(II) acetate are added to a mixture of 121.2 g (365 mmol) of 5,6-dibromo-1,1,3,3-tetramethylindane, 153.2 ml (913 mmol) of benzhydrylidenamine [1013-88-3], 96.1 g (1.0 mol) of sodium tert-butoxide and 1000 ml of toluene, and the mixture is subsequently heated under reflux for 16 h. After cooling, 500 ml of water are added, the org. phase is separated off, washed twice with 500 ml of sat. sodium chloride solution each time, the toluene is removed in a rotary evaporator, the residue is taken up in 500 ml of THF, 200 ml of 2 N hydrochloric acid are added, and the reaction mixture is heated under reflux for 16 h. The solvent is removed in vacuo, the residue is taken up in 1000 ml of ethyl acetate, the org. phase is washed with sodium hydrogencarbonate solution until pH=7 has been reached, the org. phase is dried over magnesium sulfate, the desiccant is filtered off, 500 g of silica gel are added to the filtrate, and the solvent is removed in vacuo. The loaded silica gel is placed on a silica-gel column (1500 g, slurried in n-heptane:ethyl acetate, 95:5 vv), firstly the benzophenone is eluted with n-heptane:ethyl acetate (95:5 vv), the eluent is then switched to ethyl acetate, and the product is eluted. Yield: 56.8 g (278 mmol), 76%; purity: about 95% according to .sup.1H-NMR.

(17) Variant B:

(18) A: 5,6-Dinitro-1,1,3,3-tetramethylindane, S16b

(19) ##STR00088##

(20) 350 ml of 100% by weight nitric acid are slowly added dropwise to a vigorously stirred mixture, cooled to 0° C., of 87.2 g (500 mmol) of 1,1,3,3-tetramethylindane [4834-33-7] 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 the course of 2-3 h and is then poured into a vigorously stirred mixture of 6 kg of ice and 2 kg of water. The mixture is adjusted to pH=8-9 by addition of 40% by weight NaOH, 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: 121.6 g (460 mmol), 92%; 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 can be isolated from the mother liquor.

(21) In some cases—in particular in the case of the bicyclic starting materials—the 4,5-isomer is also formed besides the 4,6-isomer in proportions of up to about 15% (see H. Tanida, J. Am. Chem. Soc. 1965, 87, 21, 4794). This can be separated off by recrystallisation or chromatography, then likewise hydrogenated and used further in the ligand synthesis. The 4,6-isomer likewise formed can be separated off by recrystallisation or chromatography, but proportions of a few % do not adversely affect the further preparation of the ligands, since the m-position of the amino functions does not allow cyclisation to give condensed ligand systems.

(22) B: 1,1,3,3-Tetramethylindane-5,6-diamine, S16

(23) 126.9 g (480 mmol) of 5,6-dinitro-1,1,3,3-tetramethylindane, S16b, are hydrogenated in 1200 ml of ethanol on 10 g of palladium/charcoal at room temperature at a hydrogen pressure of 3 bar for 24 h. The reaction mixture is filtered through a Celite bed twice, the brown solid obtained after removal of the ethanol is distilled in a bulb tube (T about 160° C., p about 10.sup.−4 mbar). Yield: 90.3 g (442 mmol), 92%; purity: about 95% according to .sup.1H-NMR.

(24) 1,1,3,3-Tetramethylindane-5,6-diamine dihydrochloride, S16×2HCl, can be obtained from S16 by dissolution in dichloromethane and introduction of gaseous HCl to saturation and subsequent removal of the dichloromethane.

(25) The following compounds can be prepared analogously:

(26) TABLE-US-00003 Variant Yield Ex. Starting material Product Step A + B S17 0 B 70% S18 A 47% S19 A 17% S20 A 21% S21 B 68% S22 00 A only step B 64% S23 01 02 B 76% S24 03 04 A 63% B 78% S25 05 06 B 80% S26 07 08 B 76% S27 09 0 B 60% S28 B 73% S29 B 77% S30 A 56% S31 A 54% S32 0 B 71% S32 A only step B 70% S33 B 75% S34 B 83% S35 B 58% S36 0 B 70% S37 A 61% S38 A only step B 36% S39 B 68% S40 B 68% S41 0 B 64% S42 B 66% S43 A 76% S44 B 76% S44 A only step B 57% S45 0 B 74% S46 B 77% S47 B 70% S48 B 59% S49 A 62% S50 0 A 60% S51 A only step B 69% S52 A only step B 74% S53 A only step B 67% S54 A 32% S55 0 A 26% S56 A 28% S57 B 57% S58 A 33% S59 B Step B 2% S60 0 B Step B 5% S61 B Step B 5% S62 B Step B 4% S63 B Step B 4% S64 B Step B 7% S65 0 B Step B 91% S66 B Step B 16%

Example S67: 7-Bromo-1,2,3,4-tetrahydro-1,4-methanonaphthalene-6-carbaldehyde, S67

(27) ##STR00193##

(28) Procedure analogous to J. Organomet. Chem., L. S. Chen et al., 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 org. phase is separated off, washed once with 500 ml of water, once with 500 ml of sat. 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.

(29) 6-Bromo-7-formyl-1,2,3,4-tetrahydro-1,4-epoxynaphthalene, S68, can be prepared analogously.

(30) ##STR00194##

(31) Use of 30.4 g (100 mmol) of 6,7-dibromo-1,2,3,4-tetrahydro-1,4-epoxynaphthalene [749859-07-2]. Yield: 14.4 g (54 mmol), 54%; purity: >95% according to .sup.1H-NMR.

Example S69: 2-(N-Pivaloylamido)benzaldehyde, S69

(32) ##STR00195##

(33) A mixture of 18.5 g (100 mmol) of 2-bromobenzaldehyde [6630-33-7], 14.2 g (140 mmol) of pivalamide [754-10-9], 81.5 g (250 mmol) of caesium carbonate, 1.7 g (3 mmol) of 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene and 630 mg (2.8 mmol) of palladium(II) acetate in 400 ml of dioxane is stirred at 100° C. for 4 h. After cooling, the solvent is removed in vacuo, the residue is taken up in 1000 ml of ethyl acetate, the org. phase is washed three times with 300 ml of water each time and once with 300 ml of sat. sodium chloride solution and filtered through a short silica-gel column. The solids obtained after the solvent has been stripped off in vacuo are reacted further. Yield: 19.3 g (94 mmol), 94%. Purity: >95% according to .sup.1H-NMR.

(34) The following derivatives can be prepared analogously:

(35) TABLE-US-00004 Bromo- Ex. arylaldehyde Amide Product Yield S70 89% S71 00 01 87% S72 02 03 04 92% S73 05 06 07 95% S74 08 09 0 94% S75 93% S76 94% S77 88% S78 0 81% S79 90% S80 91% S81 0 21% S82 27% S83 33% S84 0 93% S85 95% S86 73% S87 87% S88 0 90% S89 90% S90 67% S91 0 90% S92 92% S93 88% S94 0 94% S95 93% S96 96% S97 89% S98 0 63% S99 90%  S100 92%  S101 0 90%  S102 83%

Example S103: 7-(3,3-Dimethylbut-1-ynyl)-1,2,3,4-tetrahydro-1,4-methanonaphthalene-6-carbaldehyde, S103

(36) ##STR00295##

(37) 1.6 g (6 mmol) of triphenylphosphine, 674 mg (3 mmol) of palladium(II) acetate, 571 mg (30 mmol) of copper(I) iodide and 15.6 g (190 mmol) of tert-butylacetylene [917-92-0] 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, S67, 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 black oily residue is subjected to a bulb-tube distillation (p about 10.sup.−4 mbar, T=100-120° C.). Yield: 19.2 g (76 mmol), 76%; purity: >96% according to .sup.1H-NMR.

(38) The following derivatives can be prepared analogously:

(39) TABLE-US-00005 Bromo-aryl- Ex. aldehyde Alkyne Product Yield S104 61% S105 00 01 82% S106 02 03 04 78% S107 05 06 07 54%

Example S108: 2-tert-Butyl-4-(3,3-dimethylbut-1-ynyl)pyridine-5-carboxaldehyde, S108

(40) ##STR00308##

(41) 315 ml (315 mmol) of diisobutylaluminium hydride, 1 M in toluene, are added dropwise to a solution, cooled to −78° C., of 72.1 g (300 mmol) of 2-tert-butyl-4-(3,3-dimethylbut-1-ynyl)-5-cyanopyridine, S106, in 1500 ml of dichloromethane at such a rate that the temperature does not exceed −65° C. When the addition is complete, the reaction mixture is stirred at −78° C. for a further 2 h, then allowed to warm slowly to room temperature and stirred for a further 12 h. After re-cooling to −10° C., 300 ml of THF and then, with vigorous stirring, 230 ml of 2 N sulfuric acid (exothermic!) are added, and the mixture is stirred at room temperature for a further 12 h.

(42) After re-cooling to −10° C., a solution of 70 g of NaOH in 300 ml of water is added, the aqueous phase is separated off, the organic phase is washed three times with 1000 ml of water each time, once with 500 ml of saturated sodium chloride solution, dried over magnesium sulfate, and the solvent is removed in vacuo. Yield: 69.6 g (286 mmol), 95%. Purity: >95% according to .sup.1H-NMR.

(43) S107 is converted analogously into 2-tert-butyl-4-(2-trimethylsilyleth-1-ynyl)-5-cyanopyridine, S109. Yield: 68.7 g (268 mmol), 89%; purity: >95% according to .sup.1H-NMR.

Example S110: 2-(2-tert-Butylpyrimidin-5-yl)-5,5,7,7-tetramethyl-1,5,6,7-tetrahydroindeno[5,6-d]imidazole

(44) ##STR00309##

(45) 16.9 g (55 mmol) of oxone [70693-62-8] are added in portions with stirring at 10° C. to a solution of 16.4 g (100 mmol) of 2-tert-butylpyrimidine-5-carboxaldehyde [104461-06-5] and 22.5 g (110 mmol) of 1,1,3,3-tetramethylindane-5,6-diamine [83721-95-3], S16, in a mixture of 100 ml of DMF and 3 ml of water, and the mixture is subsequently stirred at room temperature until the aldehyde has reacted completely (about 2 h). The reaction mixture is stirred into a solution of 40 g of potassium carbonate solution in 1000 ml of water, stirred for a further 15 min., the solid formed is filtered off with suction, washed three times with 100 ml of water each time and dried in vacuo. The crude product is recrystallised from ethyl acetate/cyclohexane. Yield: 20.2 g (58 mmol), 58%. Purity: >95% according to .sup.1H-NMR.

(46) The following derivatives can be prepared analogously:

(47) TABLE-US-00006 1,2- Pyrimidine-5 Diamino- Ex. carboxaldehyde benzene Product Yield S111 0 31% S112 48% S113 45%

Example S114: 2-tert-Butyl-3-(3,3-dimethylbut-1-ynyl)pyridine-4-carboxaldehyde, S114

(48) ##STR00319##

(49) Preparation analogous to 7-(3,3-dimethylbut-1-ynyl)-1,2,3,4-tetrahydro-1,4-methanonaphthalene-6-carbaldehyde, S103. Instead of 7-bromo-1,2,3,4-tetrahydro-1,4-methanonaphthalene-6-carbaldehyde, S67, 24.2 g (100 mmol) of 2-tert-butyl-3-bromopyridine-4-carboxaldehyde [1289119-19-2] are employed. Yield: 15.3 g (63 mmol), 63%. Purity: >95% according to .sup.1H-NMR.

(50) Analogously, 24.2 g (100 mmol) of 2-tert-butyl-3-bromopyridine-4-carboxaldehyde [1289119-19-2] and 18.7 g (190 mmol) of trimethylsilylacetylene [1066-54-2] are converted into 2-tert-butyl-3-(2-trimethylsilylbut-1-ynyl)pyridine-4-carboxaldehyde, S115. Yield: 14.5 g (56 mmol), 56%; purity: >95% according to .sup.1H-NMR.

Example S116: N-(2-tert-Butyl-4-formylpyridin-3-yl)acetamide, S116

(51) ##STR00320##

(52) 7.5 ml (105 mmol) of acetyl chloride are added dropwise to a solution of 17.8 g (100 mmol) of 2-tert-butyl-3-aminopyridin-4-ylcarbaldehyde [1289036-95-8] in 100 ml of dioxane. The reaction mixture is heated under reflux for 30 min., cooled, added to 500 ml of ice-water and neutralised using sodium hydrogencarbonate. The precipitated solid is filtered off with suction, washed twice with 50 ml of water each time, dried in vacuo and then recrystallised once from DMF/EtOH. Yield: 18.7 g (85 mmol), 85%. Purity: >95% according to .sup.1H-NMR.

Example S117: 1,1,3,3-Tetramethyl-2,3-dihydro-1H-cyclopenta[c]isochromen-5-one, S117

(53) ##STR00321##

(54) Preparation analogous to A. C. Tadd et al., Chem. Commun. 2009, 6744. A mixture of 14.0 g (100 mmol) of 2,2,4,4-tetramethylcyclopentanone [4694-11-5], 28.3 g (100 mmol) of 1-bromo-2-iodobenzene [583-55-1], 97.7 g (300 mmol) of caesium carbonate, 200 g of glass beads (diameter 3 mm), 2.9 g (5 mmol) of xantphos, 1.1 g (5 mmol) of palladium(II) acetate and 500 ml of toluene is stirred at 80° C. for 24 h. A weak stream of carbon monoxide is then passed through the reaction mixture, and the temperature is increased to 110° C. so that a gentle reflux becomes established. After 16 h, the reaction mixture is allowed to cool, the salts are filtered off with suction through a Celite bed, these salts are rinsed with 1000 ml of toluene, and the filtrate is freed from toluene in vacuo. The residue is recrystallised twice from ethyl acetate/ethanol. Yield: 8.7 g (36 mmol) 36%. Purity: about 95% according to .sup.1H-NMR.

Example S118: 1,1,3,3-Tetramethyl-2,3-dihydro-1H-4-oxa-9-azacyclopenta[a]naphthalen-5-one, S118

(55) ##STR00322##

(56) Preparation analogous to S117, using 28.4 g (100 mmol) of 2-iodo-3-bromopyridine [408502-43-2] instead of 1-bromo-2-iodobenzene. Yield: 7.3 g (30 mmol), 30%. Purity: about 95% according to .sup.1H-NMR.

(57) B: Synthesis of the ligands L:

(58) 1) Ligands of the benzo[4,5]imidazo[2,1-a]isoquinoline Type

(59) General Ligand Synthesis Variant A:

(60) From 1-chloroisoquinolines and 2-haloanilines:

(61) ##STR00323##

(62) A vigorously stirred mixture of 500 mmol of the 1-chloroisoquinoline derivative, 600 mmol of the 2-haloaniline, 1250 mmol of potassium carbonate, 200 g of glass beads (diameter 3 mm), 10 mmol of triphenylphosphine and 2 mmol of palladium(II) acetate in 1500 ml of o-xylene is heated under reflux for 3-48 h until the 1-chloroisoquinoline derivative has been consumed. After cooling, the solid material is filtered off over a Celite bed, rinsed with 2000 ml of THF, and the filtrate is evaporated to dryness. The residue is dissolved in 100 ml of boiling ethyl acetate, and 800 ml of n-heptane or cyclohexane are slowly added. After cooling, the solid which has crystallised out is filtered off with suction, washed twice with 100 ml of n-heptane each time and dried in vacuo. Non-crystallising oils are chromatographed for purification. The solids or oils obtained in this way are freed from low-boiling components and non-volatile secondary components by fractional bulb-tube distillation or 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%.

Example L1: L1

(63) ##STR00324##

(64) Use of 81.8 g (500 mmol) of 1-chloroisoquinoline [19493-44-8] and 160.9 g (600 mmol) of 6-bromo-1,1,3,3-tetramethylindan-5-ylamine, S4, sublimation of the product at T about 180° C., p about 10.sup.−4 mbar. Yield: 100.6 g (320 mmol), 64%; purity: about 99.5% according to .sup.1H-NMR.

(65) The following compounds can be prepared analogously:

(66) TABLE-US-00007 1-Chloroiso- quinoline 2-Halo- Ex. derivative aniline Product Yield L2  58% L3  0 68% L4  69% L5  68% L6  56% L7  0 69% L8  64% L9  64% L10 0 59% L11 61% L12 34% L13 0 67% L14 65% L15 60% L16 61% L17 0 65% L18 67% L19 59% L20 0 60% L21 63% L22 43% L23 0 38% L24 55% L25 65% L26 63% L27 00 01 02 64% L28 03 04 05 66% L29 06 07 08 67% L30 09 0 64% L31 70% L32 69% L33 0 54% L34 67% L35 45% L36 31% L37 0 27% L38 42% L39 37% L40 0 57%
General Ligand Synthesis Variant B:
From 2-alkynylarylaldehydes and 1,2-diaminobenzenes:

(67) ##STR00442##

(68) A solution of 500 mmol of the 2-alkynylarylaldehyde and 550 mmol of the 1,2-diaminobenzene in 1000 ml of nitrobenzene is placed in an apparatus consisting of a 2000 ml one-necked flask with stopcock and attached distillation bridge and slowly heated to 200° C. (oil-bath temperature) with stirring, during which the water formed distils off. The mixture is stirred at 200° C. for a further 2 h, the temperature is then increased to about 230° C., and the nitrobenzene is distilled off in a stream of argon. Towards the end of the distillation, a vacuum of about 100 mbar is applied in order to remove final residues of nitrobenzene, the reaction mixture is then allowed to cool. If the crude product is produced in the form of a glass, the glass is mechanically comminuted, oils are mixed directly with 200-400 ml of methanol or acetonitrile, and the mixture is heated under reflux, during which the glass or oil dissolves and the product crystallises out. The crude products obtained in this way already have high purity (.sup.1H-NMR typically 97-99%). If desired, they are recrystallised again and then freed from low-boiling components and non-volatile secondary components by fractional bulb-tube distillation or 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%.

Example L41

(69) ##STR00443##

(70) Use of 72.1 g (500 mmol) of 2-(1-propyn-1-yl)benzaldehyde [176910-65-9] and 112.4 g (550 mmol) of 1,1,3,3-tetramethylindane-5,6-diamine [83721-95-3], S16, uptake of the crude product in acetonitrile, recrystallisation from ethyl acetate/methanol, sublimation of the product at T about 210° C., p about 10.sup.−4 mbar. Yield: 99.9 g (304 mmol), 61%; purity: about 99.5% according to .sup.1H-NMR.

(71) The following compounds can be prepared analogously:

(72) TABLE-US-00008 2-Alkynylaryl- 1,2-Diamino- Ex. aldehyde benzene Product Yield L42 54% L43 55% L44 0 62% L45 46% L46 48% L47 0 40% L48 51% L49 43% L50 0 52% L51 59% L52 60% L53 60% L54 0 38% L55 27% L56 58% L57 0 56% L58 43% L59 54% L60 00 55% L61 01 02 03 51% L62 04 05 06 57% L63 07 08 09 49% L64 0 40% L65 38% L66 52% L67 0 53% L68 26% L69 28% L70 0 61% L71 46% L72 20% L73 23% L74 0 21% L75 23% L76 26% L77 0 20% L78 18% L79 20% L80 0 22% L81 24% L82 23% L83 24% L84 0 26% L85 58% L86 54% L87 0 59% L88 59% L89 56% L90 0 61% L91 60% L92 23% L93 20% L94 00 01 02 24% L95 03 04 05 23%
General Ligand Synthesis Variant C:
From 1-aminoisoquinolines and 1,2-dihalobenzenes:

(73) ##STR00606##

(74) A vigorously stirred mixture of 100 mmol of the 1,2-dihalobenzene, 120 mmol of 1-aminoisoquinoline, 300 mmol of lithium bis(trimethylsilyl)amide, 100 g of glass beads (diameter 3 mm), 5 mmol of xantphos and 5 mmol of palladium(II) acetate in 600 ml of dry 1,4-dioxane is heated under reflux for 72 h until the 1-aminoisoquinoline has been consumed. For cyclisation of the secondary amine, the reaction mixture is cooled, and 10 mmol of copper(I) iodide, 20 mmol of N,N′-ethylenediamine and 230 mmol of potassium carbonate are added. The reaction mixture is refluxed again for 2-4 hours until the secondary amine has been consumed. After cooling, the solid material is filtered off over a Celite bed, rinsed with 1500 ml of dioxane, and the filtrate is evaporated to dryness. The residue is dissolved in 200 ml of dichloromethane and filtered through a silica-gel bed. The bed is rinsed with a mixture of 2000 ml of dichloromethane and 150 ml of ethyl acetate, and the filtrate is evaporated to dryness. The residue is recrystallised and dried in vacuo. The benzo[4,5]-imidazo[2,1-a]isoquinoline obtained in this way 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%.

Example L3

(75) ##STR00607##

(76) Use of 36.0 g (100 mmol) of 5,6-dibromo-1,1,2,2,3,3-hexamethylindane, S24, variant A, step A, 17.4 g (120 mmol) of 1-aminoisoquinoline [1532-84-9], 50.2 g (300 mmol) of lithium bis(trimethylsilyl)amide, 2.9 g (5 mmol) of xantphos, 1.1 g (5 mmol) of palladium(II) acetate and then 1.9 g (10 mmol) of copper(I) iodide, 1.75 g (20 mmol) of N,N′-ethylenediamine and 31.8 g (230 mmol) of potassium carbonate. The crude product is recrystallised from cyclohexane (about 15 ml/g) and sublimed in vacuo (p=10.sup.−5 mbar, T=220° C.). Yield: 20.9 g (61 mmol), 61%; purity: about 99.5% according to .sup.1H-NMR.

(77) The following compounds are prepared analogously:

(78) TABLE-US-00009 1-Aminoiso- quinoline 1,2-Dihalo- Ex. derivative benzene Product Yield L4 08 09 0 63% L7 66%
General Ligand Synthesis Variant D:
From isocoumarines and 1,2-diaminobenzenes:

(79) ##STR00614##

(80) Preparation analogous to V. K. Pandey et al., Ind. J. Chem. Section B: 1999, 38B(12), 138.

(81) A mixture of 100 mmol of the isocoumarine derivative, 110 mmol of the 1,2-diaminobenzene, 5 mmol of 4-(N,N-dimethylamino)pyridine and 200 ml of dry pyridine is boiled on a water separator, with pyridine being discharged from time to time until the pyridine has been substantially distilled off. Towards the end, a weak vacuum is applied in order to remove pyridine residues. After cooling, the viscous to glass-like residue is taken up in 200 ml of methanol and dissolved at elevated temperature, during which the product begins to crystallise. After cooling, the product is filtered off with suction and washed with a little methanol. After recrystallisation (methanol, ethanol, acetone, dioxane, DMF, etc.) of the benzo[4,5]imidazo-[2,1-a]isoquinoline 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%.

Example L276

(82) ##STR00615##

(83) Use of 24.4 g (100 mmol) of 1,1,3,3-tetramethyl-2,3-dihydro-1H-cyclopenta[c]isochromen-5-one, S117, 15.0 g (110 mmol) of 4,5-dimethyl-1,2-diaminobenzene [3171-45-7], 611 mg (5 mmol) of 4-(N,N-dimethylamino)pyridine. The crude product is recrystallised from cyclohexane (about 15 ml/g) and sublimed in vacuo (p=10.sup.−5 mbar, T=220° C.). Yield: 16.4 g (48 mmol), 48%; purity: about 99.5% according to .sup.1H-NMR.

(84) The following compounds are prepared analogously:

(85) TABLE-US-00010 1,2-Diamino- Ex. Isocoumarine benzene Product Yield L277 45% L278 0 43%
2) Ligands of the benzo[4,5]imidazo[2,1-c]quinazoline Type

(86) General Ligand Synthesis Variant A:

(87) From 2-amidoarylaldehydes and 1,2-diaminobenzenes

(88) ##STR00622##
Step A:

(89) 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.

(90) Step B:

(91) Variant A:

(92) 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.

(93) 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%.

(94) Variant B:

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

(96) Variant C:

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

Example L96

(98) ##STR00623##
Step A:

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

(100) 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 .sup.1H-NMR.

(101) Step B, Variant A:

(102) 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.

(103) General Ligand Synthesis Variant B:

(104) From 2-formamidoarylaldehydes and 1,2-diaminobenzenes

(105) ##STR00624##
Step A:

(106) Analogous to step A of the reaction of 2-amidoarylaldehydes and 1,2-diaminobenzenes.

(107) Step B:

(108) 100 mmol of the 2-(2-formamidophenyl)benzimidazole are suspended in 100 ml of dioxane. After addition of 1 ml of pyridine, 500 mmol of thionyl chloride are added dropwise to the reaction mixture, which is then stirred at room temperature until the reaction is complete (typically 24 h). the further work-up is carried out as described under step B of the reaction of 2-amidoarylaldehydes and 1,2-diaminobenzenes.

(109) The following compounds can be prepared analogously:

(110) TABLE-US-00011 2-Amidoaryl- 1,2-Diamino- Ex. aldehyde benzene Product Yield L97  55% L98  0 59% L99  61% L100 60% L101 58% L102 0 57% L103 58% L104 14% L105 0 23% L106 15% L107 43% L108 0 57% L109 55% L110 56% L111 50% L112 0 58% L113 58% L114 47% L115 0 44% L116 53% L117 49% L118 0 39% L119 50% L120 54% L121 26% L122 00 01 02 20% L123 03 04 05 51% L124 06 07 08 33% L125 09 0 30% L126 56% L127 53% L128 0 41% L129 53% L130 46% L131 18% L132 0 20% L133 13% L134 14% L135 0 56% L136 24% L137 22% L138 0 55% L139 47% L140 30% L141 48% L142 0 44% L143 25% L144 41% L145 0 54% L146 56% L147 28% L148 0 17% L149 22% L150 18% L151 32% L152 0 51% L153 46% L154 21% L155 00 01 26% L156 02 03 04 20% L157 05 06 07 16% L158 08 09 0 18% L159 23% L160 20% L161 21% L162 0 24% L163 25% L164 24% L165 0 19% L166 22%
3) Ligands of the 2,6a,11-triazabenzo[a]fluorene Type

(111) General Ligand Synthesis Variant A:

(112) From 4-alkynyl-3-formylpyridines and 1,2-diaminobenzenes:

(113) ##STR00835##

(114) A solution of 500 mmol of the 4-alkynyl-3-formylpyridine and 550 mmol of the 1,2-diaminobenzene in 1000 ml of nitrobenzene is placed in an apparatus consisting of a 2000 ml one-necked flask with stopcock and attached distillation bridge and slowly heated to 200° C. (oil-bath temperature) with stirring, during which the water formed distils off. The mixture is stirred at 200° C. for a further 2 h, the temperature is then increased to about 230° C., and the nitrobenzene is distilled off in a stream of argon. Towards the end of the distillation, a vacuum of about 100 mbar is applied in order to remove final residues of nitrobenzene, the reaction mixture is then allowed to cool. If the crude product is produced in the form of a glass, the glass is mechanically comminuted, oils are mixed directly with 200-400 ml of methanol or acetonitrile, and the mixture is heated under reflux, during which the glass or oil dissolves and the product crystallises out. The crude products obtained in this way frequently already have high purity (.sup.1H-NMR typically 97-99%). If desired, they are recrystallised again and then freed from low-boiling components and non-volatile secondary components by fractional bulb-tube distillation or sublimation (p about 10.sup.−4-10.sup.−5 mbar, T about 160-250° 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%.

Example L167

(115) ##STR00836##

(116) Use of 121.7 g (500 mmol) of S108 and 112.4 g (550 mmol) of S16. Recrystallisation of the crude product from dioxane/EtOH once, fractional sublimation of the product twice at T about 190° C., p about 10.sup.−4 mbar. Yield: 124.0 g (290 mmol), 58%; purity: >99.5% according to .sup.1H-NMR.

(117) The following compounds can be prepared analogously:

(118) TABLE-US-00012 4-Alkynyl-3-formyl- 1,2-Diamino- Ex. pyridine benzene Product Yield L168 55% L169 0 56% L170 56% L171 58% L172 0 54% L173 55% L174 55% L175 0 51% L176 24% L177 33% L178 59% L179 0 25% L180 19% L181 50% L182 0 53% L183 55% L184 49% L185 0 26% L186 18% L187 20% L188 21% L189 00 01 02 18% L190 03 04 05 19% L191 06 07 08 17%
General Ligand Synthesis Variant B:
From 2,7-naphthyridin-1-ylamines and 1,2-dihalobenzenes:

(119) ##STR00909##

(120) A vigorously stirred mixture of 100 mmol of the 1,2-dihalobenzene, 120 mmol of the 2,7-naphthyridin-1-ylamine, 300 mmol of lithium bis(trimethylsilyl)amide, 100 g of glass beads (diameter 3 mm), 5 mmol of xantphos and 5 mmol of palladium(II) acetate in 600 ml of dry 1,4-dioxane is heated under reflux for 72 h until the 1-aminoisoquinoline has been consumed. After cooling, the solid material is filtered off over a Celite bed, rinsed with 1500 ml of dioxane, and the filtrate is evaporated to dryness. The residue is dissolved in 400 ml of dichloromethane and filtered through a silica-gel bed. The bed is rinsed with a mixture of 2000 ml of dichloro methane and 150 ml of ethyl acetate, and the filtrate is evaporated to dryness. The residue is recrystallised and dried in vacuo. The 2,6a,11-triazabenzo[a]fluorene obtained in this way 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%.

Example L178

(121) ##STR00910##

(122) Use of 36.0 g (100 mmol) of 5,6-dibromo-1,1,2,2,3,3-hexamethylindane, S24, variant A, step A, 24.3 g (120 mmol) of 6-tert-butyl-2,7-naphthyridin-1-ylamine [1352329-35-1], 50.2 g (300 mmol) of lithium bis(trimethylsilyl)amide, 2.9 g (5 mmol) of xantphos and 1.1 g (5 mmol) of palladium(II) acetate. The crude product is recrystallised from ethanol (about 7 ml/g) and sublimed in vacuo (p=10.sup.−5 mbar, T=230° C.). Yield: 27.2 g (68 mmol), 68%; purity: about 99.5% according to .sup.1H-NMR.

(123) The following compounds can be prepared analogously:

(124) TABLE-US-00013 2,7-Naphthyridin- Ex. 1-ylamine 1,2-Dihalobenzene Product Yield L192 66%
4) Ligands of the 4,6a,11-triazabenzo[a]fluorene Type

(125) General Ligand Synthesis Variant A:

(126) From 2-alkynyl-3-formylpyridines and 1,2-diaminobenzenes:

(127) ##STR00914##

(128) Preparation analogous to 3) variant A, ligands of the 2,6a,11-triazabenzo[a]fluorene type.

Example L192

(129) ##STR00915##

(130) Use of 121.7 g (500 mmol) of 2-(3,3-dimethylbutyn-1-yl)-6-(1,1-dimethyl-ethyl)pyridine-3-carboxaldehyde [1352329-59-9] and 112.4 g (550 mmol) of S16. Recrystallisation of the crude product from dioxane/EtOH once, fractional sublimation of the product twice at T about 190° C., p about 10.sup.−4 mbar. Yield: 121.0 g (283 mmol), 56%; purity: >99.5% according to .sup.1H-NMR.

(131) The following derivatives can be prepared analogously:

(132) TABLE-US-00014 2-Alkynyl-3-formyl 1,2-Diamino- Ex. pyridine benzene Product Yield L193 47% L194 0 55% L195 53% L196 53% L197 0 54% L198 51% L199 49% L200 52% L201 0 55% L202 54% L203 38% L204 0 54% L205 19% L206 50% L207 0 51% L208 48% L209 20% L210 19% L211 0 20% L212 20% L213 18% L214 0 17%
General Ligand Synthesis Variant B:
From 1,6-naphthyridin-5-ylamines and 1,2-dihalobenzenes:

(133) ##STR00982##

(134) Preparation analogous to 3) variant B, ligands of the 2,6a,11-triazabenzo[a]fluorene type.

Example L204

(135) ##STR00983##

(136) Use of 36.0 g (100 mmol) of 5,6-dibromo-1,1,2,2,3,3-hexamethylindane, S24, variant A, step A, 24.3 g (120 mmol) of 2-tert-butyl-1,6-naphthyridin-5-ylamine [1352329-32-8], 50.2 g (300 mmol) of lithium bis(trimethylsilyl)amide, 2.9 g (5 mmol) of xantphos and 1.1 g (5 mmol) of palladium(II) acetate. The crude product is recrystallised from ethanol (about 7 ml/g) and sublimed in vacuo (p=10.sup.−5 mbar, T=230° C.). Yield: 26.0 g (65 mmol), 65%; purity: about 99.5% according to .sup.1H-NMR.

(137) General Ligand Synthesis Variant C:

(138) From pyrano[4,3-b]pyridin-5-ones and 1,2-aminobenzenes:

(139) ##STR00984##

(140) Preparation analogous to V. K. Pandey et al., Ind. J. Chem., Section B: 1999, 38B(12), 138.

(141) A mixture of 100 mmol of the pyrano[3,2-b]pyridin-2-one, 110 mmol of the 1,2-diaminobenzene, 5 mmol of 4-(N,N-dimethylamino)pyridine and 200 ml of dry pyridine is boiled on a water separator, with pyridine being discharged from time to time until the pyridine has been substantially distilled off. Towards the end, a weak vacuum is applied in order to remove pyridine residues. After cooling, the viscous to glass-like residue is taken up in 200 ml of methanol and dissolved at elevated temperature, with the product beginning to crystallise. After cooling, the product is filtered off with suction and washed with a little methanol. After recrystallisation (methanol, ethanol, acetone, dioxane, DMF, etc.) of the resultant 4,6a,11-triazabenzo[a]fluorene, 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%.

Example L279

(142) ##STR00985##

(143) Use of 24.3 g (100 mmol) of 1,1,3,3-tetramethyl-2,3-dihydro-1H-4-oxa-9-azacyclopenta[a]naphthalen-5-one, S118, 15.0 g (110 mmol) of 4,5-dimethyl-1,2-diaminobenzene [3171-45-7], 611 mg (5 mmol) of 4-(N,N-dimethylamino)pyridine. The crude product is recrystallised from methanol/ethyl acetate and sublimed in vacuo (p=10.sup.−5 mbar, T=220° C.). Yield: 14.7 g (43 mmol), 43%; purity: about 99.5% according to .sup.1H-NMR.

(144) The following compounds can be prepared analogously:

(145) TABLE-US-00015 Pyrano[4,3-b]- 1,2-Diamino- Ex. pyridin-5-one benzene Product Yield L280 40% L281 0 39% L282 19%
5) Ligands of the 3,6a,11-triazabenzo[a]fluorene Type

(146) General Ligand Synthesis:

(147) From 3-alkynyl-4-formylpyridines and 1,2-diaminobenzenes:

(148) ##STR00995##

(149) Preparation analogous to 3) variant A, ligands of the 2,6a,11-triazabenzo[a]fluorene type.

Example L215

(150) ##STR00996##

(151) Use of 121.7 g (500 mmol) of 2-tert-butyl-3-(3,3-dimethylbut-1-ynyl)pyridine-4-carboxaldehyde, S114, and 112.4 g (550 mmol) of S16. Recrystallisation of the crude product from dioxane/EtOH once, fractional sublimation of the product twice at T about 190° C., p about 10.sup.−4 mbar. Yield: 113.3 g (265 mmol), 53%; purity: >99.5% according to .sup.1H-NMR.

(152) The following derivatives can be prepared analogously:

(153) TABLE-US-00016 3-Alkynyl-4-formyl 1,2-Diamino- Ex. pyridine benzene Product Yield L216 54% L217 000 001 002 49% L218 003 004 005 50% L219 006 007 008 52% L220 009 010 011 53% L221 012 013 014 19% L222 015 016 017 50% L223 018 019 020 19% L224 021 022 023 18% L225 024 025 026 20%
6) Ligands of the 6a,7,11- and of the 6a,10,11-triazabenzo[a]-fluorene Type

(154) General Ligand Synthesis:

(155) From 2-alkynylarylaldehydes and 2,3-diaminopyridines:

(156) ##STR01027##

(157) Preparation analogous to 3) ligands of the 2,6a,11-triazabenzo[a]fluorene type.

Examples L226 and L227

(158) ##STR01028##

(159) Use of 134.2 g (500 mmol) of S104 and 90.9 g (550 mmol) of 2,3-diamino-6-tert-butylpyridine [893444-20-7]. Chromatographic separation of the regioisomers on silica gel (heptane:ethyl acetate, 10:1 vv), fractional sublimation of the products twice at T about 180° C., p about 10.sup.−4 mbar.

(160) Yield of L226: 41.7 g (112 mmol), 22%; purity: >99.5% according to .sup.1H-NMR.

(161) Yield of L227: 44.4 g (130 mmol), 26%; purity: >99.5% according to .sup.1H-NMR.

(162) The following derivatives can be prepared analogously:

(163) TABLE-US-00017 2-Alkynylaryl- 2,3-Diamino- Ex. aldehyde pyridine Product Yield L228 029 030 031 18% L229 032 033 034 21%
7) Ligands of the 6a,8,11- and of the 6a,9,11-triazabenzo[a]-fluorene Type

(164) General Ligand Synthesis:

(165) From 2-alkynylarylaldehydes and 3,4-diaminopyridines:

(166) ##STR01035##

(167) Preparation analogous to 3) ligands of the 2,6a,11-triazabenzo[a]fluorene type.

Examples L230 and L231

(168) ##STR01036##

(169) Use of 134.2 g (500 mmol) of S104 and 90.9 g (550 mmol) of 3,4-diamino-6-tert-butylpyridine [1237537-50-6]. Chromatographic separation of the regioisomers on silica gel (heptane:ethyl acetate, 10:1 vv), fractional sublimation of the products twice at T about 180° C., p about 10.sup.−4 mbar.

(170) Yield of L230: 48.8 g (143 mmol), 28%; purity: >99.5% according to .sup.1H-NMR.

(171) Yield of L231: 33.5 g (98 mmol), 19%; purity: >99.5% according to .sup.1H-NMR.

(172) The following derivatives can be prepared analogously:

(173) TABLE-US-00018 2-Alkynylaryl- 2,3-Diamino- Ex. aldehyde pyridine Product Yield L232 037 038 039 22% L233 040 041 042 19%
8) Ligands of the 2,5,6a,11-tetraazabenzo[a]fluorene Type

(174) General Ligand Synthesis:

(175) From 4-amido-3-cyanopyridines and 1,2-diaminobenzenes, Variant A:

(176) ##STR01043##

(177) A mixture of 100 mmol of the 4-amido-3-cyanopyridine, 210 mmol of the 1,2-diaminobenzene and 100 ml of nitrobenzene is heated stepwise to a gentle reflux and stirred until the 4-amido-3-cyanopyridine has been consumed (typically 6-16 h). The nitrobenzene is then distilled off, firstly in a stream of argon and, towards the end, by application of a vacuum (about 100 mbar). Besides the 3-(1H-benzimidazol-2-yl)pyridin-4-ylamine, the crude product obtained in this way also contains 1 eq. of 2-R-1H-benzimidazole. This mixture is reacted without further purification. After cooling under argon, glass-like residues are comminuted mechanically, oils are taken up, without further treatment, in 250 ml of dioxane or diethylene glycol dimethyl ether, 500 mmol of the corresponding carbonyl chloride and 50 mmol of the corresponding carboxylic acid are added, and the mixture is heated under reflux with vigorous stirring (precision glass stirrer) until the reacxtion is complete (typically 4-48 h). 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.) in order to remove the 1 R—C(O)-2-R-benzimidazole, the 2,5,6a,11-tetraazabenzo[a]fluorene obtained in this way is freed from low-boiling components and non-volatile secondary components by bulb-tube distillation or fractional sublimation (p about 1×10.sup.−5 mbar, T about 150-230° 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%.

(178) From 4-amido-3-cyanopyridines and 1,2-diaminobenzene dihydrochlorides, Variant B

(179) ##STR01044##

(180) A mixture, homogenised in a mortar, of 100 mmol of the 4-amido-3-cyanopyridine and 300 mmol of the 1,2-diaminobenzene dihydrochloride is adjusted in an oil bath preheated to 240° C. and left at this temperature for 3.5 h. After cooling, the deep-blue melt is dissolved in a mixture of 150 ml of ethanol and 300 ml of water at elevated temperature, and a solution of 40 g of sodium carbonate in 200 ml of water is then added dropwise with vigorous stirring (note: foaming, evolution of carbon dioxide). When the addition is complete, the mixture is stirred for a further 30 min., the grey solid is then filtered off with suction, washed three times with 100 ml of water each time and dried in vacuo. A 1:1 mixture of the 3-(1H-benzimidazol-2-yl)pyridin-4-ylamine and the 2-R-1H-benzimidazole is formed, which is cyclised as described under A without further purification and subsequently purified.

Example L234, Variant A

(181) ##STR01045##

(182) Use of 25.9 g (100 mmol) of N-(2-tert-butyl-5-cyanopyridin-4-yl)-2,2-dimethylpropionamide [1352329-37-3] and 42.9 g (210 mmol) of S16, 60.3 g (500 mmol) of pivaloyl chloride [3282-30-2], 5.1 g (50 mmol) of pivalic acid [75-98-9], 250 ml of diethylene glycol dimethyl ether, reaction time 8 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 180° C., p about 10.sup.−4 mbar. Yield: 21.1 g (51 mmol), 51%; purity: about 99.5% according to .sup.1H-NMR.

Example L234, Variant B

(183) Use of 25.9 g (100 mmol) of N-(2-tert-butyl-5-cyanopyridin-4-yl)-2,2-dimethylpropionamide [1352329-37-3] and 83.2 g (300 mmol) of S16×2 HCl, 60.3 g (500 mmol) of pivaloyl chloride [3282-30-2], 5.1 g (50 mmol) of pivalic acid [75-98-9], 250 ml of diethylene glycol dimethyl ether, reaction time 8 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 180° C., p about 10.sup.−4 mbar. Yield: 32.5 g (76 mmol), 76%; purity: about 99.5% according to .sup.1H-NMR.

(184) The following derivatives can be prepared analogously:

(185) TABLE-US-00019 2-Amido- 2,3-Diamino- Product Ex. 3-cyanopyridine benzene Variant Yield L235 046 047 048 36% L236 049 050 051 68% L237 052 053 054 65% L238 055 056 057 67% L239 058 059 060 47% L240 061 062 063 45% L241 064 065 066 27% L242 067 068 069 20%
9) Ligands of the 4,5,6a,11-tetraazabenzo[a]fluorene Type

(186) General Ligand Synthesis:

(187) From 2-amido-3-cyanopyridines and 1,2-diaminobenzenes:

(188) ##STR01070##
From 2-amido-3-cyanopyridines and 1,2-diaminobenzene dihydrochlorides, Variant B

(189) ##STR01071##

(190) Preparation analogous to 8) ligands of the 2,5,6a,11-tetraazabenzo[a]-fluorene type.

Example L243, Variant A

(191) ##STR01072##

(192) Use of 25.9 g (100 mmol) of N-(6-tert-butyl-3-cyanopyridin-2-yl)-2,2-dimethylpropionamide [1352329-36-2] and 42.9 g (210 mmol) of S16, 60.3 g (500 mmol) of pivaloyl chloride [3282-30-2], 4.1 g (40 mmol) of pivalic acid [75-98-9], 250 ml of diethylene glycol dimethyl ether, reaction time 8 h, the crude product is produced in the form of a solid on neutralisation, recrystallisation from dioxane/ethanol, fractional sublimation of the product twice at T about 180° C., p about 10.sup.−4 mbar. Yield: 20.1 g (47 mmol), 47%; purity: about 99.5% according to .sup.1H-NMR.

(193) The following derivatives can be prepared analogously:

(194) TABLE-US-00020 2-Amido- 1,2-Diamino- Ex. 3-cyanopyridine benzene Product Yield L244 073 074 075 46% L245 076 077 078 40% L246 079 080 081 48% L247 082 083 084 17%
10) Ligands of the 2,4,6a,11-tetraazabenzo[a]fluorene Type

(195) General Ligand Synthesis:

(196) From pyrimidin-5-ylbenzimidazoles and alkynes:

(197) ##STR01085##

(198) A solution of 100 mmol of the pyrimidin-5-ylbenzimidazole and 110 mmol of the alkyne in 400 ml of DMF is initially introduced in a pressure Schlenk tube, 1.5 g (4 mmol) of tetraphenylcyclopentadiene, 547 mg (1 mmol) of pentamethylcyclopentadienylrhodium chloride dimer and 21.0 g (105 mmol) of copper(II) acetate monohydrate are added, the tube is sealed, and the mixture is stirred at 100° C. for 18 h. After cooling, the DMF is removed in vacuo, the residue is taken up in 1000 ml of THF and filtered through a short silica-gel column. After removal of the THF in vacuo, the oily residue is recrystallised or chromatographed and subsequently freed from low-boiling components and non-volatile secondary components by bulb-tube distillation or fractional sublimation (p about 1×10.sup.−5 mbar, T about 150-230° 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%.

Example L248

(199) ##STR01086##

(200) Use of 34.9 g (100 mmol) of 2-(2-tert-butylpyrimidin-5-yl)-5,5,7,7-tetramethyl-1,5,6,7-tetrahydroindeno[5,6-d]imidazole, S110, and 6.0 g (110 mmol) of but-2-yne. Recrystallisation from dioxane/ethanol, fractional sublimation of the product twice at T about 200° C., p about 10.sup.−4 mbar.

(201) Yield: 10.8 g (27 mmol), 27%; purity: about 99.5% according to .sup.1H-NMR.

(202) The following derivatives can be prepared analogously:

(203) TABLE-US-00021 2-(2-tert- Butylpyrimidin- Ex. 5-yl)benzimidazole Alkyne Product Yield L249 087 088 089 31% L250 090 091 092 26% L251 093 094 095 33%
11) Ligands of the 3,5,6a,11-tetraazabenzo[a]fluorene Type

(204) General Ligand Synthesis:

(205) From 3-amido-4-formylpyridines and 1,2-diaminobenzenes:

(206) ##STR01096##

(207) Preparation analogous to 2) ligands of the benzo[4,5]imidazo[2,1-c]quinazoline type.

Example L252, Variant A

(208) ##STR01097##
Step A:

(209) Use of 22.0 g (100 mmol) of S116 and 22.5 g (110 mmol) of S16.

(210) The N-[2-tert-butyl-4-(5,5,7,7-tetramethyl-1,5,6,7-tetrahydroindeno[5,6-d]-imidazol-2-yl)pyridin-3-yl]acetamide crystallises out, yield 33.6 g (83 mmol), 83%; purity: 97% according to .sup.1H-NMR.

(211) Step B, Variant A:

(212) Use of 33.6 g (83 mmol) of N-[2-tert-butyl-4-(5,5,7,7-tetramethyl-1,5,6,7-tetrahydroindeno[5,6-d]imidazol-2-yl)pyridin-3-yl]acetamide (step A), 100 ml of dioxane, 20.0 ml (280 mmol) of acetyl chloride [75-36-5] and 2.3 ml (40 mmol) of acetic acid [64-19-7], reaction time 16 h, the crude product is produced in the form of a solid on neutralisation, recrystallisation from dioxane/ethanol, fractional sublimation of the product twice at T about 180° C., p about 10.sup.−4 mbar. Yield: 21.6 g (56 mmol), 68%; purity: about 99.5% according to .sup.1H-NMR.

(213) The following derivatives can be prepared analogously:

(214) TABLE-US-00022 3-Amido- 1,2-Diamino- Product Ex. 4-formylpyridine benzene Variant Yield L253 098 099 00 52% L254 01 02 03 55% L255 04 05 06 52% L256 07 08 09 48% L257 0 44% L258 18%
12) Ligands of the 5,6a,7,11- and 5,6a,10,11-tetraazabenzo[a]fluorene Type

(215) General Ligand Synthesis Variant A:

(216) From 2-amidoarylaldehydes and 2,3-diaminopyridines

(217) ##STR01116##

(218) Preparation analogous to 2) ligands of the benzo[4,5]imidazo[2,1-c]-quinazoline type.

Examples L259 and L260, Variant A

(219) ##STR01117##
Step A:

(220) Use of 27.1 g (100 mmol) of S99 and 18.2 g (110 mmol) of 2,3-diamino-6-tert-butylpyridine [893444-20-7]. The N-[7-(5-tert-butyl-3H-imidazo[4,5-b]-pyridin-2-yl)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-6-yl]-2,2-dimethylpropanamide crystallises out. Yield: 32.1 g (77 mmol), 77%; purity: 97% according to .sup.1H-NMR.

(221) Step B, Variant A:

(222) Use of 32.1 g (77 mmol) of N-[7-(5-tert-butyl-3H-imidazo[4,5-b]pyridin-2-yl)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-6-yl]-2,2-dimethylpropanamide (step A), 100 ml of dioxane, 31.4 g (260 mmol) of pivaloyl chloride [3282-30-2] and 3.8 g (37 mmol) of pivalic acid [75-98-9], reaction time 18 h, the crude product is produced in the form of a solid on neutralisation. Chromatographic separation of the regioisomers on silica gel (heptane:ethyl acetate, 10:1 vv), fractional sublimation of the products twice at T about 180° C., p about 10.sup.−4 mbar.

(223) Yield of L259: 9.1 g (23 mmol), 30%; purity: >99.5% according to .sup.1H-NMR.

(224) Yield of L260: 7.2 g (18 mmol), 23%; purity: >99.5% according to .sup.1H-NMR.

(225) The following derivatives can be prepared analogously:

(226) TABLE-US-00023 2-Amido- 2,3-Diamino- Product Ex. arylaldehyde pyridine Variant Yield L261 0 25% L262 21%
13) Ligands of the 5,6a,8,11- and 5,6a,9,11-tetraazabenzo[a]fluorene Type

(227) General Ligand Synthesis Variant A:

(228) From 2-amidoarylaldehydes and 3,4-diaminopyridines:

(229) ##STR01124##

(230) Preparation analogous to 2) ligands of the benzo[4,5]imidazo[2,1-c]-quinazoline type.

Examples L263 and L264, Variant A

(231) ##STR01125##
Step A:

(232) Use of 27.1 g (100 mmol) of S99 and 18.2 g (110 mmol) of 3,4-diamino-6-tert-butylpyridine [1237537-50-6]. The N-[7-(6-tert-butyl-3H-imidazo[4,5-c]pyridin-2-yl)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-6-yl]-2,2-dimethylpropanamide crystallises out. Yield: 28.8 g (69 mmol), 77%; purity: 97% according to .sup.1H-NMR.

(233) Step B, Variant A:

(234) Use of 28.8 g (69 mmol) of N-[7-(6-tert-butyl-3H-imidazo[4,5-c]pyridin-2-yl)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-6-yl]-2,2-dimethylpropanamide (step A), 100 ml of dioxane, 27.9 g (230 mmol) of pivaloyl chloride [3282-30-2] and 3.4 g (33 mmol) of pivalic acid [75-98-9], reaction time 18 h, the crude product is produced in the form of a solid on neutralisation. Chromatographic separation of the regioisomers on silica gel (heptane:ethyl acetate, 10:1 vv), fractional sublimation of the products twice at T about 180° C., p about 10.sup.−4 mbar.

(235) Yield of L263: 7.2 g (18 mmol), 26%; purity: >99.5% according to .sup.1H-NMR.

(236) Yield of L264: 6.4 g (16 mmol), 23%; purity: >99.5% according to .sup.1H-NMR.

(237) The following derivatives can be prepared analogously:

(238) TABLE-US-00024 2-Amido- 3,4-Diamino- Product Ex. arylaldehyde pyridine Variant Yield L265 25% L266 0 16%
14) Ligands of the 6a,7,9,11- and 6a,8,10,11-tetraazabenzo[a]fluorene Type

(239) General Ligand Synthesis:

(240) From 2-amidoarylaldehydes and 5,6-diaminopyrimidines:

(241) ##STR01132##

(242) Preparation analogous to 3) ligands of the 2,6a,11-triazabenzo[a]-fluorene type.

Examples L267 and L268

(243) ##STR01133##

(244) Use of 134.2 g (500 mmol) of S104 and 90.9 g (550 mmol) of 2-tert-butyl-5,6-diaminopyrimidine [18202-78-3]. Chromatographic separation of the regioisomers on silica gel (heptane:ethyl acetate, 10:1 vv), fractional sublimation of the products twice at T about 180° C., p about 10.sup.−4 mbar.

(245) Yield of L267: 53.4 g (156 mmol), 31%; purity: >99.5% according to .sup.1H-NMR.

(246) Yield of L268: 34.6 g (101 mmol), 20%; purity: >99.5% according to .sup.1H-NMR.

(247) The following derivatives can be prepared analogously:

(248) TABLE-US-00025 2-Alkynylaryl- 5,6-Diamino- Ex. aldehyde pyrimidine Product Yield L269 26% L270 23%
15) Ligands of the 2,4,5,6a,11-pentaazabenzo[a]fluorene Type

(249) General Ligand Synthesis:

(250) From 4-amido-5-methoxycarbonylpyrimidines and 1,2-diaminobenzene dihydrochlorides

(251) ##STR01140##

(252) Preparation analogous to 8) variant B ligands of the 2,5,6a,11-tetraazabenzo[a]fluorene type, where the 4-amido-5-methoxycarbonylpyrimidines are employed instead of the 4-amido-3-cyanopyridines.

Example L271

(253) ##STR01141##

(254) Use of 29.3 g (100 mmol) of methyl 2-tert-butyl-4-(2,2-dimethylpropylamido)pyrimidine-5-carboxylate [1352329-45-3] and 83.2 g (300 mmol) of S16×2 HCl, 60.3 g (500 mmol) of pivaloyl chloride [3282-30-2], 5.1 g (50 mmol) of pivalic acid [75-98-9], 250 ml of diethylene glycol dimethyl ether, reaction time 8 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 190° C., p about 10.sup.−4 mbar. Yield: 28.4 g (66 mmol), 66%; purity: about 99.5% according to .sup.1H-NMR.

(255) The following derivatives can be prepared analogously:

(256) TABLE-US-00026 4-Amido- 5-methoxy- 1,2-Diamino- carbonyl- benzene Ex. pyrimidine dihydrochloride Product Yield L272 63% L273 58% L274 0 55% L275 19%
16) Ligands of the imidazo[1,2-f]phenanthridine Type

(257) General Ligand Synthesis Variant A:

(258) From 6-aminophenanthridines and 2-haloketones:

(259) ##STR01154##

(260) A mixture of 100 mmol of the 6-aminophenanthridine derivative, 300 mmol of the haloketone, 300 mmol of sodium hydrogencarbonate, 300 ml of ethylene glycol and 30 ml of water is stirred at 130° C. for 24 h. A further 300 mmol of the 2-haloketone and 300 mmol of sodium hydrogencarbonate are then added, and the mixture is stirred at 130° C. for a further 24 h. After cooling, the reaction mixture is diluted with 1000 ml of water, extracted three times with 300 ml of ethyl acetate or dichloromethane each time, the combined organic phases are washed with 500 ml of water and with 500 ml of saturated sodium chloride solution, the org. phase is evaporated in vacuo, and the residue is recrystallised or chromatographed on silica gel. The solids or oils obtained in this way are freed from low-boiling components and non-volatile secondary components by fractional bulb-tube distillation or 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%.

(261) General Ligand Synthesis Variant B:

(262) From 6-aminophenanthridines and 1,2-dihaloolefins:

(263) ##STR01155##

(264) A mixture of 100 mmol of the 6-aminophenanthridine derivative, 200 mmol of the 1,2-dihaloolefin, 300 mmol of potassium carbonate, 5 mmol of palladium(II) acetate, 30 mmol of triphenylphosphine, 100 g of glass beads (diameter 3 mm) and 200 ml of o-xylene is heated under reflux with vigorous stirring until (typically 6-24 h) the 6-amino-phenanthridine has been consumed. After cooling to 80° C., the salts and glass beads are filtered off with suction over a Celite bed, rinsed with 300 ml of hot o-xylene, the filtrate is evaporated to dryness in vacuo, and the residue is recrystallised or chromatographed on silica gel. The solids or oils obtained in this way are freed from low-boiling components and non-volatile secondary components by fractional bulb-tube distillation or sublimation (p about 10.sup.−4-10.sup.−5 mbar, T about 160-240° C.). Purity according to .sup.1H-NMR typically >99.5%.

Example L500

(265) ##STR01156##
Variant A:

(266) Use of 19.4 g (100 mmol) of 6-aminophenanthridine [832-68-8] and 43.4 g (300 mmol) of 3-chloro-(1R,3R,4S)-bicyclo[2.2.1]heptan-2-one [10464-71-8], chromatography on silica gel (ethyl acetate:dichloromethane 80:20 vv), then recrystallisation from DMF/ethanol, fractional sublimation of the product twice at T about 190° C., p about 10.sup.−4 mbar. Yield: 5.4 g (19 mmol), 19%; purity: about 99.5% according to .sup.1H-NMR.

(267) Variant B:

(268) Use of 19.4 g (100 mmol) of 6-aminophenanthridine [832-68-8] and 50.4 g (200 mmol) of 2,3-dibromobicyclo[2.2.1]hept-2-ene [75267-72-0], chromatography on silica gel (ethyl acetate:dichloromethane 80:20 vv), then recrystallisation from DMF/ethanol, fractional sublimation of the product twice at T about 190° C., p about 10.sup.−4 mbar. Yield: 10.8 g (38 mmol), 38%; purity: about 99.5% according to .sup.1H-NMR.

(269) The following derivatives can be prepared analogously:

(270) TABLE-US-00027 2-Haloketone 6-Amino- or 1,2-dihalo- Ex. phenanthridine olefin Product Yield L501 13% L502 0 34% L503 28% L504 29% L505 0 35% L506 34% L507 37% L508 0 35% L509 32% L510 27%
17) Ligands of the 8b,13-diazaindeno[1,2-l]phenanthrene Type

(271) General Ligand Synthesis Variant A:

(272) From 6-aminophenanthridines and 1,2-dihalobenzenes:

(273) ##STR01187##

(274) A vigorously stirred mixture of 100 mmol of the 6-aminophenanthridine derivative, 130 mmol of the 1,2-dihalobenzene, 130 mmol of potassium carbonate, 100 g of glass beads (diameter 3 mm), 8 mmol of triphenylphosphine and 2 mmol of palladium(II) acetate in 300 ml of o-xylene is heated under reflux for 3-48 h until the 6-aminophenanthridine derivative has been consumed. After cooling to 80° C., the salts and glass beads are filtered off with suction over a Celite bed, rinsed with 500 ml of hot o-xylene, the filtrate is evaporated to dryness in vacuo, and the residue is recrystallised or chromatographed on silica gel. The solids or oils obtained in this way are freed from low-boiling components and non-volatile secondary components by fractional bulb-tube distillation or 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%.

(275) General Ligand Synthesis Variant B:

(276) From 6-halophenanthridines and 1-amino-2-halobenzenes:

(277) ##STR01188##

(278) Preparation analogous to 1) ligands of the benzo[4,5]imidazo[2,1-a]-isoquinoline type.

Example L511

(279) ##STR01189##
Variant B:

(280) Use of 213.67 g (100 mmol) of 6-chlorophenanthridine [15679-03-5] and 35.6 g (120 mmol) of S6, recrystallisation from dioxane/ethanol, fractional sublimation of the product twice at T about 210° C., p about 10.sup.−4 mbar.

(281) Yield: 22.8 g (58 mmol), 58%; purity: about 99.5% according to .sup.1H-NMR.

(282) General Ligand Synthesis Variant C:

(283) From 6-aminophenanthridines and 1,2-dihalobenzenes:

(284) ##STR01190##

(285) Preparation analogous to 1) variant C, ligands of the benzo[4,5]imidazo[2,1-a]isoquinoline type.

Example L511

(286) ##STR01191##

(287) Use of 36.0 g (100 mmol) of 5,6-dibromo-1,1,2,2,3,3-hexamethylindane, S24, variant A, step A, 23.3 g (120 mmol) of 6-aminophenanthridine [832-68-8], 50.2 g (300 mmol) of lithium bis(trimethylsilyl)amide, 2.9 g (5 mmol) of xantphos, 1.1 g (5 mmol) of palladium(II) acetate and then 1.9 g (10 mmol) of copper(I) iodide, 1.75 g (20 mmol) of N,N′-ethylenediamine and 31.8 g (230 mmol) of potassium carbonate. The crude product is recrystallised from dioxane (about 5 ml/g) and sublimed in vacuo (p=10.sup.−5 mbar, T=240° C.). Yield: 25.5 g (65 mmol), 65%; purity: about 99.5% according to .sup.1H-NMR.

(288) The following derivatives can be prepared analogously:

(289) TABLE-US-00028 1,2-Dihalo- or 1-amino- Product Ex. Phenanthridine 2-halobenzene Variant Yield L512 53% L513 48% L514 00 52% L515 01 02 03 40% L516 04 05 06 55% L517 07 08 09 58% L518 0 50%
18) Tetradentate Ligands, L283

(290) ##STR01213##
A) L282-Br

(291) ##STR01214##

(292) 19.6 g (110 mmol) of NBS are added in portions to a solution, warmed to 100° C., of 37.2 g (100 mmol) of L282 in 300 ml of DMF, and the mixture is subsequently stirred for a further 6 h. The reaction mixture is evaporated to about 150 ml in vacuo, stirred for a further 2 h, the deposited crystals are filtered off with suction and finally washed twice with 50 ml of methanol each time and dried in vacuo. Yield: 35.6 g (79 mmol), 79%. Purity: 97% according to .sup.1H-NMR.

(293) B) L282-B

(294) ##STR01215##

(295) 20 ml (50 mmol) of n-butyllithium (2.5 M in hexane) are added dropwise with vigorous stirring to a solution, cooled to −78° C., of 22.5 g (50 mmol) of L282-Br in 500 ml of THF, and the mixture is stirred for a further 30 min. 5.6 ml (50 mmol) of trimethyl borate are added to this solution in one portion, the mixture is stirred for a further 1 h and then allowed to warm to room temperature. The solvent is removed in vacuo, and the residue is employed in the Suzuki coupling C).

(296) C) Suzuki Coupling

(297) A mixture of 22.5 g (50 mmol) of L282-Br and 20.7 g (50 mmol) of L282-B—as obtained under B)—31.8 g (150 mmol) of tripotassium phosphate, 1.8 g (6 mmol) of tri-o-tolylphosphine, 224 mg (1 mmol) of palladium(II) acetate, 300 ml of toluene, 100 ml of dioxane and 300 ml of water is heated under reflux for 12 h. After cooling, the precipitated solid is filtered off with suction, washed twice with 50 ml of toluene each time and three times with 100 ml of ethanol each time. The crude product is recrystallised from sulfolane (about 5 ml/g) and sublimed in vacuo (p=10.sup.−5 mbar, T=300° C.). Yield: 21.9 g (29 mmol), 58%; purity: about 99.5% according to .sup.1H-NMR.

(298) 19) Hexadentate Ligands, L284

(299) ##STR01216##
A) L282-OH

(300) ##STR01217##

(301) 20 ml (50 mmol) of n-butyllithium (2.5 M in hexane) are added dropwise with vigorous stirring to a solution, cooled to −78° C., of 22.5 g (50 mmol) of L282-Br in 500 ml of THF, and the mixture is stirred for a further 30 min. 5.6 ml (50 mmol) of trimethyl borate are added to this solution in one portion, the mixture is stirred for a further 1 h and then allowed to warm to room temperature. The solvent is removed in vacuo, the residue is taken up in 1000 ml of ethyl acetate, the solution is cooled to 5° C., 32 ml of aqueous H.sub.2O.sub.2 solution (30% by weight) are added with vigorous stirring, and a solution of 1.4 g of NaOH in 30 ml of water is then added dropwise. After stirring for 3 h, 500 ml of saturated ammonium chloride solution are added, the organic phase is separated off, washed twice with 200 ml of water each time, dried over magnesium sulfate, and the organic phase is then evaporated to a volume of about 50 ml in vacuo. 200 ml of methanol are added to the crystal slurry, the crystals are filtered off with suction, washed once with 50 ml of methanol and dried in vacuo. Yield: 13.5 g (35 mmol), 70%. Purity: 95% according to .sup.1H-NMR.

(302) B) L284

(303) 1.6 g (40 mmol) of sodium hydride, 60% dispersion in mineral oil, are added in portions to a vigorously stirred solution of 13.5 g (35 mmol) of L282-OH in 100 ml of THF (note: evolution of hydrogen, foaming). When the evolution of hydrogen is complete, 3.1 g (10 mmol) of 1,1,1-tris(bromomethyl)ethane [60111-68-4] are added, and the reaction mixture is heated under reflux for 16 h. After cooling, the THF is removed in vacuo, the residue is taken up in 500 ml of ethyl acetate, washed three times with 200 ml of water each time and once with 100 ml of saturated sodium chloride solution, and the organic phase is dried over sodium sulfate. The residue obtained after removal of the solvent is chromatographed on silica gel (ethyl acetate:n-heptane, 5:1 vv) and then dried in vacuo. Yield: 7.1 g (5.8 mmol), 58%. Purity: 99% according to .sup.1H-NMR.

(304) C: Synthesis of the Metal Complexes:

(305) 1) Homoleptic Tris-Facial Iridium Complexes:

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

(307) 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 300-400° C., with the sublimation preferably being carried out in the form of a fractional sublimation. 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 Λ,Δ in point group C3 generally has significantly lower solubility in the extractant than that in point group C1, 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 C1 are employed in enantiomerically pure form, the enantiomer pair Λ,Δ in point group C3 is formed.

(308) Variant B: Tris-(2,2,6,6-tetramethyl-3,5-heptanedionato)iridium(III) as Iridium Starting Material

(309) 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.

(310) TABLE-US-00029 Variant Reaction temp./ reaction time Ligand Ir complex Suspension medium Ex. L Diastereomer Extractant Yield Ir(L1).sub.3 L1 A 260° C./100 h DCM Mesitylene 40% Ir(L1).sub.3 L1 B 280° C./100 h DCM Mesitylene 48% Ir(L2).sub.3 L2 Ir(L2).sub.3 B 43% 290° C./100 h DCM Mesitylene Ir(L3).sub.3 L3 Ir(L3).sub.3 as Ex. Ir(L1).sub.3/B 43% Ir(L4).sub.3 L4 Ir(L4).sub.3 as Ex. Ir(L1).sub.3/B 45% Ir(L5).sub.3 L5 Ir(L5).sub.3 as Ex. Ir(L1).sub.3/B 40% Ir(L6).sub.3 L6 Ir(L6).sub.3 as Ex. Ir(L1).sub.3/B 47% Ir(L7).sub.3 L7 Ir(L7).sub.3 as Ex. Ir(L1).sub.3/B 25% Λ,Δ-C3 Ir(L8).sub.3 L8 Ir(L8).sub.3 as Ex. Ir(L1).sub.3/B 25% Λ,Δ-C3 Ir(L9).sub.3 L9 Ir(L9).sub.3 B 41% 280° C./150 h DCM Mesitylene Ir(L10).sub.3 L10 Ir(L10).sub.3 as Ex. Ir(L1).sub.3/B 43% Ir(L11).sub.3 L11 Ir(L11).sub.3 as Ex. Ir(L1).sub.3/B 24% Λ,Δ-C3 Ir(L12).sub.3 L12 Ir(L12).sub.3 as Ex. Ir(L1).sub.3/B  7% Λ,Δ-C3 Ir(L13).sub.3 L13 Ir(L13).sub.3 as Ex. Ir(L1).sub.3/B 26% Λ,Δ-C3 Ir(L14).sub.3 L14 Ir(L14).sub.3 as Ex. Ir(L1).sub.3/B 45% Ir(L15).sub.3 L15 Ir(L15).sub.3 as Ex. Ir(L1).sub.3/B 47% Ir(L16).sub.3 L16 Ir(L16).sub.3 B 43% 280° C./180 h DCM Mesitylene Ir(L17).sub.3 L17 Ir(L17).sub.3 as Ex. Ir(L16).sub.3 38% Ir(L18).sub.3 L18 Ir(L18).sub.3 as Ex. Ir(L1).sub.3/B 45% Ir(L19).sub.3 L19 Ir(L19).sub.3 as Ex. Ir(L1).sub.3/B 21% Λ,Δ-C3 Ir(L20).sub.3 L20 Ir(L20).sub.3 as Ex. Ir(L1).sub.3/B 45% Ir(L21).sub.3 L21 Ir(L21).sub.3 as Ex. Ir(L1).sub.3/B 23% Λ,Δ-C3 Ir(L22).sub.3 L22 Ir(L22).sub.3 as Ex. Ir(L1).sub.3/B 23% Ir(L23).sub.3 L23 Ir(L23).sub.3 as Ex. Ir(L16).sub.3 21% Ir(L24).sub.3 L24 Ir(L24).sub.3 as Ex. Ir(L1).sub.3/B 26% Λ,Δ-C3 Ir(L25).sub.3 L25 Ir(L25).sub.3 as Ex. Ir(L16).sub.3 27% Λ,Δ-C3 Ir(L26).sub.3 L26 Ir(L26).sub.3 as Ex. Ir(L1).sub.3/B 44% Ir(L27).sub.3 L27 Ir(L27).sub.3 as Ex. Ir(L1).sub.3/B 48% Ir(L28).sub.3 L28 Ir(L28).sub.3 as Ex. Ir(L1).sub.3/B 47% Ir(L29).sub.3 L29 Ir(L29).sub.3 as Ex. Ir(L16).sub.3 37% Ir(L30).sub.3 L30 Ir(L30).sub.3 as Ex. Ir(L16).sub.3 35% Ir(L31).sub.3 L31 Ir(L31).sub.3 as Ex. Ir(L2).sub.3 26% Λ,Δ-C3 Ir(L32).sub.3 L32 Ir(L32).sub.3 as Ex. Ir(L2).sub.3 50% Ir(L33).sub.3 L33 Ir(L33).sub.3 as Ex. Ir(L2).sub.3 43% Ir(L34).sub.3 L34 Ir(L34).sub.3 as Ex. Ir(L2).sub.3 51% Ir(L35).sub.3 L35 Ir(L35).sub.3 as Ex. Ir(L1).sub.3/B 21% Ir(L36).sub.3 L36 Ir(L36).sub.3 as Ex. Ir(L1).sub.3/B 19% Ir(L37).sub.3 L37 Ir(L37).sub.3 as Ex. Ir(L16).sub.3 30% Ir(L38).sub.3 L38 Ir(L38).sub.3 as Ex. Ir(L16).sub.3 17% Ir(L39).sub.3 L39 Ir(L39).sub.3 as Ex. Ir(L1).sub.3/B 39% Ir(L40).sub.3 L40 Ir(L40).sub.3 as Ex. Ir(L1).sub.3/B 37% Ir(L41).sub.3 L41 Ir(L41).sub.3 as Ex. Ir(L1).sub.3/B 46% Ir(L42).sub.3 L42 Ir(L42).sub.3 as Ex. Ir(L1).sub.3/B 36% Ir(L43).sub.3 L43 Ir(L43).sub.3 as Ex. Ir(L1).sub.3/B 33% Ir(L44).sub.3 L44 Ir(L44).sub.3 as Ex. Ir(L16).sub.3  4% Ir(L45).sub.3 L45 Ir(L45).sub.3 as Ex. Ir(L2).sub.3 43% Ir(L46).sub.3 L46 Ir(L46).sub.3 as Ex. Ir(L1).sub.3/B 45% Λ,Δ-C3 + C1 Ir(L47).sub.3 L47 Ir(L47).sub.3 as Ex. Ir(L1).sub.3/B 23% Ir(L48).sub.3 L48 Ir(L48).sub.3 as Ex. Ir(L1).sub.3/B 36% Ir(L49).sub.3 L49 Ir(L49).sub.3 as Ex. Ir(L1).sub.3/B 39% Ir(L50).sub.3 L50 Ir(L50).sub.3 as Ex. Ir(L1).sub.3/B 38% Ir(L51).sub.3 L51 Ir(L51).sub.3 as Ex. Ir(L1).sub.3/B 50% Ir(L52).sub.3 L52 Ir(L52).sub.3 as Ex. Ir(L1).sub.3/B 48% Ir(L53).sub.3 L53 Ir(L53).sub.3 as Ex. Ir(L1).sub.3/B 48% Ir(L54).sub.3 L54 Ir(L54).sub.3 as Ex. Ir(L1).sub.3/B 34% Ir(L55).sub.3 L55 Ir(L55).sub.3 as Ex. Ir(L1).sub.3/B 41% Λ,Δ-C3 + C1 Ir(L56).sub.3 L56 Ir(L56).sub.3 as Ex. Ir(L1).sub.3/B 40% Ir(L57).sub.3 L57 Ir(L57).sub.3 as Ex. Ir(L1).sub.3/B 24% Λ,Δ-C3 Ir(L58).sub.3 L58 Ir(L58).sub.3 as Ex. Ir(L1).sub.3/B 17% Λ,Δ-C3 Ir(L59).sub.3 L59 Ir(L59).sub.3 as Ex. Ir(L16).sub.3  2% Λ,Δ-C3 Ir(L60).sub.3 L60 Ir(L60).sub.3 as Ex. Ir(L1).sub.3/B 23% Λ,Δ-C3 Ir(L61).sub.3 L61 Ir(L61).sub.3 as Ex. Ir(L1).sub.3/B 18% Λ,Δ-C3 Ir(L62).sub.3 L62 Ir(L62).sub.3 as Ex. Ir(L2).sub.3 40% Ir(L63).sub.3 L63 Ir(L63).sub.3 as Ex. Ir(L1).sub.3/B 41% Ir(L64).sub.3 L64 Ir(L64).sub.3 as Ex. Ir(L1).sub.3/B 34% Ir(L65).sub.3 L65 Ir(L65).sub.3 as Ex. Ir(L1).sub.3/B 17% Λ,Δ-C3 Ir(L66).sub.3 L66 Ir(L66).sub.3 as Ex. Ir(L1).sub.3/B 23% Λ,Δ-C3 Ir(L67).sub.3 L67 Ir(L67).sub.3 as Ex. Ir(L1).sub.3/B 19% Λ,Δ-C3 Ir(L68).sub.3 L68 Ir(L68).sub.3 as Ex. Ir(L16).sub.3 12% Λ,Δ-C3 Ir(L69).sub.3 L69 Ir(L69).sub.3 as Ex. Ir(L16).sub.3 16% Λ,Δ-C3 Ir(L70).sub.3 L70 Ir(L70).sub.3 as Ex. Ir(L1).sub.3/B 21% Λ,Δ-C3 Ir(L71).sub.3 L71 Ir(L71).sub.3 as Ex. Ir(L1).sub.3/B 18% Λ,Δ-C3 Ir(L72).sub.3 L72 Ir(L72).sub.3 as Ex. Ir(L1).sub.3/B  9% Λ,Δ-C3 Ir(L73).sub.3 L73 Ir(L73).sub.3 as Ex. Ir(L1).sub.3/B 17% Ir(L74).sub.3 L74 Ir(L74).sub.3 as Ex. Ir(L1).sub.3/B 46% Ir(L75).sub.3 L75 Ir(L75).sub.3 as Ex. Ir(L1).sub.3/B 46% Ir(L76).sub.3 L76 Ir(L76).sub.3 as Ex. Ir(L1).sub.3/B 48% Ir(L77).sub.3 L77 Ir(L77).sub.3 as Ex. Ir(L1).sub.3/B 45% Ir(L78).sub.3 L78 Ir(L78).sub.3 as Ex. Ir(L16).sub.3 33% Ir(L79).sub.3 L79 Ir(L79).sub.3 as Ex. Ir(L16).sub.3 30% Ir(L80).sub.3 L80 Ir(L80).sub.3 as Ex. Ir(L1).sub.3/B 44% Ir(L81).sub.3 L81 Ir(L81).sub.3 as Ex. Ir(L1).sub.3/B 45% Ir(L82).sub.3 L82 Ir(L82).sub.3 as Ex. Ir(L1).sub.3/B 22% Λ,Δ-C3 Ir(L83).sub.3 L83 Ir(L83).sub.3 as Ex. Ir(L1).sub.3/B 26% Λ,Δ-C3 Ir(L84).sub.3 L84 Ir(L84).sub.3 as Ex. Ir(L2).sub.3 51% Ir(L85).sub.3 L85 Ir(L85).sub.3 as Ex. Ir(L16).sub.3 23% Λ,Δ-C3 Ir(L85).sub.3 L85 Ir(L85).sub.3 as Ex. Ir(L16).sub.3  9% C1 Ir(L86).sub.3 L86 Ir(L86).sub.3 as Ex. Ir(L16).sub.3 28% Λ,Δ-C3 Ir(L87).sub.3 L87 Ir(L87).sub.3 as Ex. Ir(L16).sub.3 25% Λ,Δ-C3 Ir(L88).sub.3 L88 Ir(L88).sub.3 as Ex. Ir(L16).sub.3 27% Λ,Δ-C3 Ir(L89).sub.3 L89 Ir(L89).sub.3 as Ex. Ir(L16).sub.3 24% Λ,Δ-C3 Ir(L90).sub.3 L90 Ir(L90).sub.3 as Ex. Ir(L16).sub.3 26% Λ,Δ-C3 Ir(L91).sub.3 L91 Ir(L91).sub.3 as Ex. Ir(L16).sub.3 28% Λ,Δ-C3 Ir(L92).sub.3 L92 Ir(L92).sub.3 as Ex. Ir(L1).sub.3/B 42% Ir(L93).sub.3 L93 Ir(L93).sub.3 as Ex. Ir(L1).sub.3/B 45% Ir(L94).sub.3 L94 Ir(L94).sub.3 as Ex. Ir(L16).sub.3 29% Λ,Δ-C3 Ir(L95).sub.3 L95 Ir(L95).sub.3 as Ex. Ir(L16).sub.3 22% Λ,Δ-C3 Ir(L276).sub.3 L276 Ir(L276).sub.3 as Ex. Ir(L1).sub.3/B 40% Ir(L277) L277 Ir(L277).sub.3 as Ex. Ir(L1).sub.3/B 38% Ir(L278).sub.3 L278 Ir(L278).sub.3 as Ex. Ir(L1).sub.3/B 22% Λ,Δ-C3 Ir(L96).sub.3 L96 0 B 300° C./100 h DCM Mesitylene 46% Ir(L97).sub.3 L97 Ir(L97).sub.3 as Ex. Ir(L96).sub.3 40% Ir(L98).sub.3 L98 Ir(L98).sub.3 B 38% 300° C./180 h DCM Mesitylene Ir(L99).sub.3 L99 Ir(L99).sub.3 as Ex. Ir(L98).sub.3 31% Ir(L100).sub.3 L100 Ir(L100).sub.3 as Ex. Ir(L96).sub.3 48% Ir(L101).sub.3 L101 Ir(L101).sub.3 as Ex. Ir(L98).sub.3 32% Ir(L102).sub.3 L102 Ir(L102).sub.3 as Ex. Ir(L96).sub.3 50% Ir(L103).sub.3 L103 Ir(L103).sub.3 as Ex. Ir(L98).sub.3 19% Λ,Δ-C3 Ir(L104).sub.3 L104 Ir(L104).sub.3 as Ex. Ir(L96).sub.3 22% Λ,Δ-C3 Ir(L105).sub.3 L105 Ir(L105).sub.3 as Ex. Ir(L96).sub.3 36% Λ,Δ-C3 + C1 Ir(L106).sub.3 L106 Ir(L106).sub.3 as Ex. Ir(L98).sub.3 28% Λ,Δ-C3 Ir(L107).sub.3 L107 Ir(L107).sub.3 as Ex. Ir(L98).sub.3 31% Ir(L108).sub.3 L108 Ir(L108).sub.3 as Ex. Ir(L96).sub.3 33% Λ,Δ-C3 + C1 Ir(L109).sub.3 L109 Ir(L109).sub.3 as Ex. Ir(L96).sub.3 49% Ir(L110).sub.3 L110 Ir(L110).sub.3 as Ex. Ir(L98).sub.3 35% Ir(L111).sub.3 L111 Ir(L111).sub.3 as Ex. Ir(L96).sub.3 44% Ir(L112).sub.3 L112 Ir(L112).sub.3 as Ex. Ir(L96).sub.3 43% Ir(L113).sub.3 L113 Ir(L113).sub.3 as Ex. Ir(L96).sub.3 44% Ir(L114).sub.3 L113 Ir(L114).sub.3 as Ex. Ir(L96).sub.3 39% Ir(L115).sub.3 L113 Ir(L115).sub.3 as Ex. Ir(L96).sub.3 40% Ir(L116).sub.3 L116 Ir(L116).sub.3 as Ex. Ir(L96).sub.3 37% Ir(L117).sub.3 L117 Ir(L117).sub.3 as Ex. Ir(L98).sub.3 28% Ir(L118).sub.3 L118 Ir(L118).sub.3 as Ex. Ir(L96).sub.3 40% Ir(L119).sub.3 L119 Ir(L119).sub.3 as Ex. Ir(L98).sub.3 44% Ir(L120).sub.3 L120 Ir(L120).sub.3 as Ex. Ir(L98).sub.3 45% Ir(L121).sub.3 L121 Ir(L121).sub.3 as Ex. Ir(L98).sub.3 18% Ir(L122).sub.3 L122 Ir(L122).sub.3 as Ex. Ir(L96).sub.3 19% Λ,Δ-C3 Ir(L123).sub.3 L123 Ir(L123).sub.3 as Ex. Ir(L96).sub.3 36% Ir(L124).sub.3 L124 Ir(L124).sub.3 as Ex. Ir(L96).sub.3 37% Ir(L125).sub.3 L125 Ir(L125).sub.3 as Ex. Ir(L96).sub.3 41% Ir(L126).sub.3 L126 Ir(L126).sub.3 as Ex. Ir(L96).sub.3 24% Λ,Δ-C3 Ir(L127).sub.3 L127 Ir(L127).sub.3 as Ex. Ir(L98).sub.3 19% Λ,Δ-C3 Ir(L128).sub.3 L128 Ir(L128).sub.3 as Ex. Ir(L98).sub.3 17% Λ,Δ-C3 Ir(L129).sub.3 L129 Ir(L129).sub.3 as Ex. Ir(L96).sub.3 23% Λ,Δ-C3 Ir(L130).sub.3 L130 Ir(L130).sub.3 as Ex. Ir(L96).sub.3 22% Λ,Δ-C3 Ir(L131).sub.3 L131 Ir(L131).sub.3 as Ex. Ir(L98).sub.3 22% Λ,Δ-C3 Ir(L132).sub.3 L132 Ir(L132).sub.3 as Ex. Ir(L96).sub.3 24% Λ,Δ-C3 Ir(L133).sub.3 L133 Ir(L133).sub.3 as Ex. Ir(L96).sub.3 25% Λ,Δ-C3 Ir(L134).sub.3 L134 Ir(L134).sub.3 as Ex. Ir(L98).sub.3 21% Λ,Δ-C3 Ir(L135).sub.3 L135 Ir(L135).sub.3 as Ex. Ir(L96).sub.3 21% Λ,Δ-C3 Ir(L136).sub.3 L136 Ir(L136).sub.3 as Ex. Ir(L96).sub.3 24% Λ,Δ-C3 Ir(L137).sub.3 L137 Ir(L137).sub.3 as Ex. Ir(L96).sub.3 17% Λ,Δ-C3 Ir(L138).sub.3 L138 Ir(L138).sub.3 as Ex. Ir(L98).sub.3 22% Λ,Δ-C3 Ir(L139).sub.3 L139 Ir(L139).sub.3 as Ex. Ir(L96).sub.3 21% Λ,Δ-C3 Ir(L140).sub.3 L140 Ir(L140).sub.3 as Ex. Ir(L96).sub.3 14% Λ,Δ-C3 Ir(L141).sub.3 L141 Ir(L141).sub.3 as Ex. Ir(L98).sub.3 23% Λ,Δ-C3 Ir(L142).sub.3 L142 Ir(L142).sub.3 as Ex. Ir(L98).sub.3 39% Ir(L143).sub.3 L143 Ir(L143).sub.3 as Ex. Ir(L96).sub.3 45% Ir(L144).sub.3 L144 Ir(L144).sub.3 as Ex. Ir(L96).sub.3 36% Ir(L145).sub.3 L145 Ir(L145).sub.3 as Ex. Ir(L96).sub.3 18% Λ,Δ-C3 Ir(L146).sub.3 L146 Ir(L146).sub.3 as Ex. Ir(L98).sub.3 24% Λ,Δ-C3 Ir(L147).sub.3 L147 Ir(L147).sub.3 as Ex. Ir(L96).sub.3 18% Λ,Δ-C3 Ir(L148).sub.3 L148 Ir(L148).sub.3 as Ex. Ir(L96).sub.3 19% Λ,Δ-C3 Ir(L149).sub.3 L149 Ir(L149).sub.3 as Ex. Ir(L98).sub.3 15% Λ,Δ-C3 Ir(L150).sub.3 L150 Ir(L150).sub.3 as Ex. Ir(L98).sub.3  6% Λ,Δ-C3 Ir(L151).sub.3 L151 Ir(L151).sub.3 as Ex. Ir(L96).sub.3 16% Λ,Δ-C3 Ir(L152).sub.3 L152 Ir(L152).sub.3 as Ex. Ir(L96).sub.3 46% Λ,Δ-C3 Ir(L153).sub.3 L153 Ir(L153).sub.3 as Ex. Ir(L98).sub.3 10% Λ,Δ-C3 Ir(L154).sub.3 L154 Ir(L154).sub.3 as Ex. Ir(L96).sub.3  8% Λ,Δ-C3 Ir(L155).sub.3 L155 Ir(L155).sub.3 as Ex. Ir(L96).sub.3 23% Ir(L156).sub.3 L156 Ir(L156).sub.3 as Ex. Ir(L96).sub.3 14% Ir(L157).sub.3 L157 Ir(L157).sub.3 as Ex. Ir(L96).sub.3 48% Ir(L158).sub.3 L158 Ir(L158).sub.3 as Ex. Ir(L96).sub.3 46% Ir(L159).sub.3 L159 Ir(L159).sub.3 as Ex. Ir(L96).sub.3 47% Ir(L160).sub.3 L160 Ir(L160).sub.3 as Ex. Ir(L96).sub.3 47% Ir(L161).sub.3 L161 Ir(L161).sub.3 as Ex. Ir(L96).sub.3 44% Ir(L162).sub.3 L162 Ir(L162).sub.3 as Ex. Ir(L96).sub.3 40% Ir(L163).sub.3 L163 Ir(L163).sub.3 as Ex. Ir(L96).sub.3 26% Λ,Δ-C3 Ir(L164).sub.3 L164 Ir(L164).sub.3 as Ex. Ir(L96).sub.3 25% Λ,Δ-C3 Ir(L165).sub.3 L165 Ir(L165).sub.3 as Ex. Ir(L96).sub.3 43% Ir(L166).sub.3 L166 Ir(L166).sub.3 as Ex. Ir(L96).sub.3 48% Ir(L167).sub.3 L167 B 310° C./180 h DCM Mesitylene 44% Ir(L168).sub.3 L168 Ir(L168).sub.3 B 38% 310° C./200 h DCM Mesitylene Ir(L169).sub.3 L169 Ir(L169).sub.3 as Ex. Ir(L167).sub.3 46% Ir(L170).sub.3 L170 Ir(L170).sub.3 as Ex. Ir(L167).sub.3 44% Ir(L171).sub.3 L171 Ir(L171).sub.3 as Ex. Ir(L167).sub.3 43% Ir(L172).sub.3 L172 Ir(L172).sub.3 as Ex. Ir(L167).sub.3 20% Λ,Δ-C3 Ir(L173).sub.3 L173 Ir(L173).sub.3 as Ex. Ir(L167).sub.3 25% Λ,Δ-C3 Ir(L174).sub.3 L174 Ir(L174).sub.3 as Ex. Ir(L167).sub.3 45% Ir(L175).sub.3 L175 Ir(L175).sub.3 as Ex. Ir(L167).sub.3 23% Λ,Δ-C3 Ir(L176).sub.3 L176 Ir(L176.sub.3 as Ex. Ir(168).sub.3 18% Λ,Δ-C3 Ir(L177).sub.3 L177 Ir(L177).sub.3 as Ex. Ir(L167).sub.3 21% Ir(L178).sub.3 L178 Ir(L178).sub.3 as Ex. Ir(L167).sub.3 42% Ir(L179).sub.3 L179 Ir(L179).sub.3 as Ex. Ir(L167).sub.3 43% Ir(L180).sub.3 L180 Ir(L180).sub.3 as Ex. Ir(L167).sub.3 45% Λ,Δ-C3 + 1 Ir(L181).sub.3 L181 Ir(L181).sub.3 as Ex. Ir(L167).sub.3 26% Λ,Δ-C3 Ir(L182).sub.3 L182 Ir(L182).sub.3 as Ex. Ir(167).sub.3 20% Λ,Δ-C3 Ir(L183).sub.3 L183 Ir(L183).sub.3 as Ex. Ir(L167).sub.3 36% Ir(L184).sub.3 L184 Ir(L184).sub.3 as Ex. Ir(L167).sub.3 18% Λ,Δ-C3 Ir(L185).sub.3 L185 Ir(L185).sub.3 as Ex. Ir(L167).sub.3 12% Ir(L186).sub.3 L186 Ir(L186).sub.3 as Ex. Ir(L167).sub.3 45% Ir(L187).sub.3 L187 Ir(L187).sub.3 as Ex. Ir(L167).sub.3 45% Ir(L188).sub.3 L188 Ir(L188).sub.3 as Ex. Ir(L167).sub.3 47% Ir(L189).sub.3 L189 Ir(L189).sub.3 as Ex. Ir(L167).sub.3 41% Ir(L190).sub.3 L190 Ir(L190).sub.3 as Ex. Ir(L167).sub.3 23% Λ,Δ-C3 Ir(L191).sub.3 L191 Ir(L191).sub.3 as Ex. Ir(L167).sub.3 44% Ir(L192).sub.3 L192 B 305° C./180 h Acetone Mesitylene 46% Ir(L193).sub.3 L193 Ir(L193).sub.3 B 36% 310° C./210 h Acetone Mesitylene Ir(L194).sub.3 L194 Ir(L194).sub.3 as Ex. Ir(L192).sub.3 46% Ir(L195).sub.3 L195 Ir(L195).sub.3 as Ex. Ir(L193).sub.3 3.5%  Ir(L196).sub.3 L196 Ir(L196).sub.3 as Ex. Ir(L192).sub.3 44% Ir(L197).sub.3 L197 Ir(L197).sub.3 as Ex. Ir(L192).sub.3 45% Ir(L198).sub.3 L198 Ir(L198).sub.3 as Ex. Ir(L192).sub.3 27% Λ,Δ-C3 Ir(L199).sub.3 L199 Ir(L199).sub.3 as Ex. IrL(193).sub.3 26% Λ,Δ-C3 Ir(L200).sub.3 L200 Ir(L200).sub.3 as Ex. Ir(L192).sub.3 21% Λ,Δ-C3 Ir(L201).sub.3 L201 Ir(L201).sub.3 as Ex. Ir(L192).sub.3 42% Ir(L202).sub.3 L202 Ir(L202).sub.3 as Ex. Ir(L192).sub.3 26% Λ,Δ-C3 Ir(L203).sub.3 L203 Ir(L203).sub.3 as Ex. Ir(L192).sub.3 28% Ir(L204).sub.3 L204 Ir(L204).sub.3 as Ex. Ir(L192).sub.3 45% Ir(L205).sub.3 L205 Ir(L205).sub.3 as Ex. Ir(L192).sub.3 45% Λ,Δ-C3 + C1 Ir(L206).sub.3 L206 Ir(L206).sub.3 as Ex. Ir(L192).sub.3 20% Λ,Δ-C3 Ir(L207).sub.3 L207 Ir(L207).sub.3 as Ex. Ir(L192).sub.3 23% Λ,Δ-C3 Ir(L208).sub.3 L208 Ir(L208).sub.3 as Ex. Ir(L192).sub.3 25% Λ,Δ-C3 Ir(L209).sub.3 L209 Ir(L209).sub.3 as Ex. Ir(L192).sub.3 44% Ir(L210).sub.3 L210 Ir(L210).sub.3 as Ex. Ir(L192).sub.3 43% Ir(L211).sub.3 L211 Ir(L211).sub.3 as Ex. Ir(L192).sub.3 46% Ir(L212).sub.3 L212 Ir(L212).sub.3 as Ex. Ir(L192).sub.3 46% Ir(L213).sub.3 L213 Ir(L213).sub.3 as Ex. Ir(L192).sub.3 21% Λ,Δ-C3 Ir(L214).sub.3 L214 Ir(L214).sub.3 as Ex. Ir(L192).sub.3 37% Ir(L279).sub.3 L279 Ir(L279).sub.3 as Ex. Ir(L192).sub.3 40% Ir(L280).sub.3 L280 Ir(L280).sub.3 as Ex. Ir(L192).sub.3 37% Ir(L281).sub.3 L281 Ir(L281).sub.3 as Ex. Ir(L192).sub.3 19% Λ,Δ-C3 Ir(L282).sub.3 L282 Ir(L282).sub.3 as Ex. Ir(L192).sub.3 33% Ir(L284) L284 Ir(L284) as Ex. Ir(192).sub.3 16% 10 mmol Addition of 1 ml of tridecane Ir(L215).sub.3 L215 B 305° C./180 h Acetone Mesitylene 45% Ir(L216).sub.3 L216 Ir(L216).sub.3 B 34% 310° C./210 h Acetone Mesitylene Ir(L217).sub.3 L217 Ir(L217).sub.3 as Ex. Ir(L215).sub.3 44% Ir(L218).sub.3 L218 Ir(L218).sub.3 as Ex. Ir(L215).sub.3 46% Ir(L219).sub.3 L219 Ir(L219).sub.3 as Ex. Ir(L215).sub.3 22% Λ,Δ-C3 Ir(L220).sub.3 L220 Ir(L220).sub.3 as Ex. Ir(L215).sub.3 45% Ir(L221).sub.3 L221 Ir(L221).sub.3 as Ex. Ir(L215).sub.3 44% Λ,Δ-C3 + C1 Ir(L222).sub.3 L222 Ir(L222).sub.3 as Ex. Ir(L215).sub.3 21% Λ,Δ-C3 Ir(L223).sub.3 L223 Ir(L223).sub.3 as Ex. Ir(L215).sub.3 41% Ir(L224).sub.3 L224 Ir(L224).sub.3 as Ex. Ir(L215).sub.3 20% Λ,Δ-C3 Ir(L225).sub.3 L225 Ir(L225).sub.3 as Ex. Ir(L215).sub.3 35% Ir(L226).sub.3 L226 B 300° C./200 h Acetone Mesitylene 22% Ir(L227).sub.3 L227 as Ex. Ir(L226).sub.3 24% Ir(L228).sub.3 L228 Ir(L228).sub.3 as Ex. Ir(L226).sub.3 19% Λ,Δ-C3 Ir(L229).sub.3 L229 Ir(L229).sub.3 as Ex. Ir(L226).sub.3 17% Λ,Δ-C3 Ir(L230).sub.3 L230 B 300° C./200 h Acetone Mesitylene 23% Ir(L231).sub.3 L231 as Ex. Ir(L230).sub.3 21% Ir(L232).sub.3 L232 Ir(L232).sub.3 as Ex. Ir(L230).sub.3 22% Λ,Δ-C3 Ir(L233).sub.3 L233 Ir(L233).sub.3 as Ex. Ir(L230).sub.3 24% Λ,Δ-C3 Ir(L234).sub.3 L234 B 310° C./180 h Acetone Mesitylene 40% Ir(L235).sub.3 L235 Ir(L235).sub.3 B 30% 310° C./210 h Acetone Mesitylene Ir(L236).sub.3 L236 Ir(L236).sub.3 as Ex. Ir(L234).sub.3 38% Ir(L237).sub.3 L237 Ir(L237).sub.3 as Ex. Ir(L234).sub.3 37% Ir(L238).sub.3 L238 Ir(L238).sub.3 as Ex. Ir(L234).sub.3 18% Λ,Δ-C3 Ir(L239).sub.3 L230 Ir(L239).sub.3 as Ex. Ir(L234).sub.3 33% Ir(L240).sub.3 L240 Ir(L240).sub.3 as Ex. Ir(L234).sub.3 21% Λ,Δ-C3 Ir(L241).sub.3 L241 Ir(L241).sub.3 as Ex. Ir(L234).sub.3 16% Λ,Δ-C3 Ir(L242).sub.3 L242 Ir(L242).sub.3 as Ex. Ir(L234).sub.3 31% Ir(L243).sub.3 L243 B 310° C./210 h THF Mesitylene 16% Ir(L244).sub.3 L244 Ir(L244).sub.3 B 14% 315° C./210 h Acetone Mesitylene Ir(L245).sub.3 L245 Ir(L245).sub.3 as Ex. Ir(L243).sub.3 18% Ir(L246).sub.3 L246 Ir(L246).sub.3 as Ex. Ir(L243).sub.3  9% Λ,Δ-C3 Ir(L247).sub.3 L247 Ir(L247).sub.3 as Ex. Ir(L243).sub.3  7% Ir(L248).sub.3 L248 0 B 310° C./210 h Acetone Mesitylene 16% Ir(L249).sub.3 L249 Ir(L249).sub.3 B  8% 315° C./240 h Acetone Mesitylene Ir(L250).sub.3 L250 Ir(L250).sub.3 as Ex. Ir(L248).sub.3 17% Ir(L251).sub.3 L251 Ir(L251).sub.3 as Ex. Ir(L248).sub.3  6% Λ,Δ-C3 Ir(L252).sub.3 L252 B 310° C./210 h Acetone Mesitylene 35% Ir(L253).sub.3 L253 Ir(L253).sub.3 as Ex. Ir(L252).sub.3 20% Ir(L254).sub.3 L254 Ir(L254).sub.3 as Ex. Ir(L252).sub.3 36% Ir(L255).sub.3 L255 Ir(L255).sub.3 as Ex. Ir(L252).sub.3 34% Ir(L256).sub.3 L256 Ir(L256).sub.3 as Ex. Ir(L252).sub.3 17% Λ,Δ-C3 Ir(L257).sub.3 L257 Ir(L257).sub.3 as Ex. Ir(L252).sub.3 18% Λ,Δ-C3 Ir(L258).sub.3 L258 Ir(L258).sub.3 as Ex. Ir(L252).sub.3 24% Ir(L259).sub.3 L259 B 310° C./200 h Acetone Mesitylene 21% Ir(L260).sub.3 L260 as Ex. Ir(L259).sub.3 19% Ir(L261).sub.3 L261 Ir(L261).sub.3 as Ex. Ir(L259).sub.3 18% Λ,Δ-C3 Ir(L262).sub.3 L262 Ir(L262).sub.3 as Ex. Ir(L259).sub.3 16% Λ,Δ-C3 Ir(L263).sub.3 L263 B 310° C./200 h Acetone Mesitylene 20% Ir(L264).sub.3 L264 as Ex. Ir(L263).sub.3 18% Ir(L265).sub.3 L265 Ir(L265).sub.3 as Ex. Ir(L263).sub.3 16% Λ,Δ-C3 Ir(L266).sub.3 L266 Ir(L266).sub.3 as Ex. Ir(L263).sub.3 15% Λ,Δ-C3 Ir(L267).sub.3 L267 B 310° C./220 h Acetone Mesitylene 15% Ir(L268).sub.3 L268 B 310° C./220 h Acetone Mesitylene 13% Ir(L269).sub.3 L269 Ir(L269).sub.3 as Ex. Ir(L267).sub.3 16% Λ,Δ-C3 Ir(L270).sub.3 L270 Ir(L270).sub.3 as Ex. Ir(L267).sub.3 16% Λ,Δ-C3 Ir(L271).sub.3 L271 B 320° C./200 h Acetone Mesitylene  8% Ir(L272).sub.3 L272 Ir(L272).sub.3 as Ex. Ir(L271).sub.3  2% Ir(L273).sub.3 L273 Ir(L273).sub.3 as Ex. Ir(L271).sub.3  6% Ir(L274).sub.3 L274 Ir(L274).sub.3 as Ex. Ir(L271).sub.3  6% Λ,Δ-C3 + C1 Ir(L275).sub.3 L275 Ir(L275).sub.3 as Ex. Ir(L271).sub.3  4% Ir(L500).sub.3 L500 B 270° C./100 h THF Mesitylene 44% Ir(L501).sub.3 L502 Ir(L501).sub.3 as Ex. Ir(L500).sub.3 21% Λ,Δ-C3 Ir(L502).sub.3 L503 Ir(L502).sub.3 as Ex. Ir(L500).sub.3 20% Λ,Δ-C3 Ir(L503).sub.3 L504 Ir(L503).sub.3 as Ex. Ir(L500).sub.3 23% Λ,Δ-C3 Ir(L504).sub.3 L505 Ir(L504).sub.3 as Ex. Ir(L500).sub.3 25% Λ,Δ-C3 Ir(L505).sub.3 L506 Ir(L505).sub.3 as Ex. Ir(L500).sub.3 19% Λ,Δ-C3 Ir(L506).sub.3 L507 Ir(L506).sub.3 as Ex. Ir(L500).sub.3 20% Λ,Δ-C3 Ir(L507).sub.3 L508 Ir(L507).sub.3 as Ex. Ir(L500).sub.3 22% Λ,Δ-C3 Ir(L508).sub.3 L509 Ir(L508).sub.3 as Ex. Ir(L500).sub.3 22% Λ,Δ-C3 Ir(L509).sub.3 L509 Ir(L509).sub.3 as Ex. Ir(L500).sub.3 26% Λ,Δ-C3 Ir(L510).sub.3 L510 Ir(L510).sub.3 as Ex. Ir(L500).sub.3 11% Λ,Δ-C3 Ir(L511).sub.3 L511 0 B 280° C./150 h Acetone Mesitylene 56% Ir(L512).sub.3 L512 Ir(L512).sub.3 B 45% 300° C./150 h DCM Mesitylene Ir(L513).sub.3 L513 Ir(L513).sub.3 as Ex. Ir(L511).sub.3 49% Ir(L514).sub.3 L514 Ir(L514).sub.3 as Ex. Ir(L511).sub.3 23% Λ,Δ-C3 Ir(L515).sub.3 L515 Ir(L515).sub.3 as Ex. Ir(L511).sub.3 19% Λ,Δ-C3 Ir(L516).sub.3 L516 Ir(L516).sub.3 as Ex. Ir(L511).sub.3 51% Ir(L517).sub.3 L517 Ir(L517).sub.3 as Ex. Ir(L511).sub.3 50% Ir(L518).sub.3 L518 Ir(L518).sub.3 as Ex. Ir(L511).sub.3 21% Λ,Δ-C3
2) Heteroleptic Iridium Complexes:
Variant A:
Step 1:

(311) A mixture of 10 mmol of sodium bisacetylacetonatodichloroiridate(III) [770720-50-8] and 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 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 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 DCM, 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.

(312) Step 2:

(313) The crude chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 obtained in this way is suspended in a mixture of 75 ml of 2-ethoxyethanol and 25 ml of water, 13 mmol of the co-ligand CL or the co-ligand compound CL and 15 mmol of sodium carbonate are added. After 20 h under reflux, a further 75 ml of water are added dropwise, after cooling the solid is filtered off with suction, washed three times with 50 ml of water each time and three times with 50 ml of methanol each time and dried in vacuo. The dry solid is placed on an aluminium oxide bed (aluminium oxide, basic activity grade 1) with a depth of 3-5 cm in a continuous hot extractor and then extracted with the extraction medium indicated (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 extraction medium is evaporated to about 100 ml in vacuo. Metal complexes which have excessively good solubility in the extraction medium 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, if a purity of 99.5-99.9% has been reached, the metal complex is heated or sublimed. Besides the hot extraction method for purification, the purification can also be carried out by chromatography on silica gel or aluminium oxide. The heating is carried out in the temperature range from about 200-300° C. in a high vacuum (p about 10.sup.−6 mbar). The sublimation is carried out in the temperature range from about 300-400° C. in a high vacuum (p about 10.sup.−6 mbar), where the sublimation is preferably carried out in the form of a fractional sublimation.

(314) TABLE-US-00030 Ir complex Ligand Co-ligand Step 1: reaction temp./reaction time/suspension medium Ex. L CL Step 2: extractant Yield Ir(L3).sub.2(CL1) L3 48% Ir(L16).sub.2(CL1)  L16 CL1 45% Ir(L32).sub.2(CL1)  L32 CL1 56% Ir(L79).sub.2(CL2)  L79 39% Ir(L98).sub.2(CL2)  L98 CL2 54% Ir(L113).sub.2(CL2)  L113 CL2 60% Ir(L127).sub.2(CL3)  L127 0 47% Ir(L158).sub.2(CL4)  L158 44% Ir(L169).sub.2(CL5)  L169 50% Ir(L195).sub.2(CL7)  L195 47%
Variant B:
Step 1:

(315) See variant A, step 1.

(316) Step 2:

(317) The crude chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 obtained in this way is suspended in 200 ml of THF, 20 mmol of co-ligand CL, 20 mmol of silver(I) trifluoroacetate and 30 mmol of potassium carbonate are added to the suspension, and the mixture is heated under reflux for 24 h. After cooling, the THF is removed in vacuo. The residue is taken up in 200 ml of a mixture of ethanol and conc. ammonia solution (1:1, vv). The suspension is stirred at room temperature for 1 h, the solid is filtered off with suction, washed twice with 50 ml of a mixture of ethanol and conc. ammonia solution (1:1, vv) each time and twice with 50 ml of ethanol each time and then dried in vacuo. Hot extraction and sublimation as in variant A.

(318) TABLE-US-00031 Ir complex Ligand Co-ligand Step 1: reaction temp./reaction time/suspension medium Ex. L CL Step 2: extractant Yield Ir(L99).sub.2(CL7) L99  39% Ir(L110).sub.2(CL8) L110 0 31% Ir(L158).sub.2(CL8) L158 39% Ir(L195).sub.2(CL10) L195 38%
Variant C:
Step 1:

(319) See variant A, step 1.

(320) Step 2:

(321) The crude chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 obtained in this way is suspended in 1000 ml of dichloromethane and 150 ml of ethanol, 20 mmol of silver(I) trifluoromethanesulfonate are added to the suspension, and the mixture is stirred at room temperature for 24 h. The precipitated solid (AgCl) is filtered off with suction via a short Celite bed, and the filtrate is evaporated to dryness in vacuo. The solid obtained in this way is taken up in 100 ml of ethylene glycol, 20 mmol of co-ligand CL are added, and the mixture is then stirred at 130° C. for 30 h. After cooling, the solid is filtered off with suction, washed twice with 50 ml of ethanol each time and dried in vacuo. Hot extraction and sublimation as in variant A.

(322) TABLE-US-00032 Ir complex Ligand Co-ligand Step 1: reaction temp./reaction time/suspension medium Ex. L CL Step 2: extractant Yield Ir(L191).sub.2(CL11) L191 46% Ir(L201).sub.2(CL11) L201 CL11 39% Ir(L220).sub.2(CL12) L220 44%
Variant E:

(323) A mixture of 10 mmol of the Ir complex Ir(L).sub.2(CL1 or CL2) and 20 mmol of ligand L and a glass-clad magnetic stirrer bar is melted into a 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. Further work-up, purification and sublimation as described under 1) Homoleptic tris-facial iridium complexes.

(324) TABLE-US-00033 Ir complex Ir complex Ligand Step 1: reaction temp./reaction time/suspension medium Ex. Ir(L).sub.2(CL) L′ Step 2: extractant Yield Ir(L3).sub.2(L9) Ir(L3).sub.2(CL1) L9  0 39% Ir(L98).sub.2(L53) Ir(L98).sub.2(CL2) L53  43% Ir(L113).sub.2(L109) Ir(L113).sub.2(CL2) L109 44% Ir(L113).sub.2(L204) Ir(L113).sub.2(CL2) L204 36%
3) Heteroleptic Platinum Complexes:

(325) A mixture of 10 mmol of platinum(II) chloride and 12 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 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 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 DCM, acetone, ethyl acetate, toluene, etc.) and mechanically digested at the same time. The fine suspension is decanted off from the glass beads, the solid is filtered off with suction and dried in vacuo. The crude chloro dimer of the formula [Pt(L)Cl].sub.2 obtained in this way is suspended in a mixture of 60 ml of 2-ethoxyethanol and 20 ml of water, and 20 mmol of co-ligand CL or co-ligand compound CL and 20 mmol of sodium carbonate are added. After 20 h under reflux, a further 100 ml of water are added dropwise, after cooling the solid is filtered off with suction, washed three times with 50 ml of water each time and three times with 50 ml of methanol each time and dried in vacuo. The solid obtained in this way is placed on a Celite bed with a depth of 3-5 cm in a hot extractor and then extracted with the extraction medium indicated (initially introduced amount about 500 ml). When the extraction is complete, the extraction medium is evaporated to about 100 ml in vacuo. Metal complexes which have excessively good solubility in the extraction medium 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, if a purity of 99.5-99.9% has been reached, the metal complex is heated or sublimed. The heating is carried out in the temperature range from about 200-300° C. in a high vacuum (p about 10.sup.−6 mbar). The sublimation is carried out in the temperature range from about 250-350° C. in a high vacuum (p about 10.sup.−6 mbar), where the sublimation is preferably carried out in the form of a fractional sublimation.

(326) TABLE-US-00034 Ligand Co-ligand Ex. L CL Pt complex Yield Pt(L3)(CL1) L3  CL1 20% Pt(L126)(CL2) L126 CL2 23%
4) Platinum Complexes of Tetradentate Ligands:
Variant A:

(327) A mixture of 10 mmol of bis(benzonitrile)platinum(II) dichloride and 10 mmol of ligand L in 100 ml of benzonitrile is heated under reflux for 24 h. After dropwise addition of 100 ml of methanol to the cooled reaction mixture, the solid is filtered off with suction, washed five times with 25 ml of methanol each time and dried in vacuo. The solid obtained in this way is placed on a Celite bed (aluminium oxide, basic activity grade 1) with a depth of 3 cm in a hot extractor and then extracted with the extraction medium indicated (initially introduced amount about 300 ml). When the extraction is complete, the extraction medium is evaporated to about 100 ml in vacuo. Metal complexes which have excessively good solubility in the extraction medium 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; if a purity of 99.5-99.9% has been reached, the Pt complex is sublimed. The sublimation is carried out in the temperature range from about 350 to about 390° C. in a high vacuum (p about 10.sup.−6 mbar), where the sublimation is preferably carried out in the form of a fractional sublimation.

(328) Pt(L283):

(329) ##STR01276##

(330) Use of 4.74 g (10 mmol) of bis(benzonitrile)platinum(II) dichloride and 7.55 g (10 mmol) of L283. Extractant: mesitylene. Yield: 3.22 g (3.4 mmol), 34%; purity: about 99.8% according to NMR.

(331) E: Derivatisation of the Metal Complexes:

(332) 1) Halogenation of the Iridium Complexes:

(333) A×11 mmol of N-halosuccinimide (halogen: CI, Br, I) are added to a solution or suspension of 10 mmol of a complex carrying A×C—H groups (where A=1, 2 or 3) in the para-position to the iridium in 3000 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.

(334) Synthesis of Ir(L1-Br).sub.3:

(335) ##STR01277##

(336) 5.9 g (33 mmol) of N-bromosuccinimide are added in one portion to a suspension, stirred at 30° C., of 11.3 g (10 mmol) of Ir(L1).sub.3 in 3000 ml of DCM, and the mixture is then stirred for a further 20 h. After removal of about 2900 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: 13.8 g (9.7 mmol), 97%; purity: about 99.5% according to NMR.

(337) The following compounds can be prepared analogously:

(338) TABLE-US-00035 Ex. Complex Brominated complex Yield Ir(L3-Br).sub.3 95% Ir(L8-Br).sub.3 0 96% Ir(L10-Br).sub.3 95% Ir(L55-Br).sub.3 91% Ir(L96-Br).sub.3 98% Ir(L120-Br).sub.3 96% Ir(L126-Br).sub.3 0 97% Ir(L113).sub.2(L109-Br) 95%
2) Suzuki Coupling on the Iridium Complexes:
Variant A, Two-Phase Reaction Mixture:

(339) 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 org. phase is washed three times with 200 ml of water, once with 200 ml of sat. 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.

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

(341) 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, di-tert-butylphosphine, 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 A.

(342) Synthesis of Ir(L276).sub.3:

(343) ##STR01294##
Variant B:

(344) Use of 14.5 g (10 mmol) of Ir(L1-Br).sub.3 and 14.0 g (40 mmol) of quaterphenyl-boronic acid [1233200-59-3], caesium carbonate, tri-ortho-tolylphosphine, NMP, 180° C., 1 h. Yield: 12.1 g (5.9 mmol), 59%; purity: about 99.8% according to HPLC.

(345) The following compounds can be prepared analogously:

(346) TABLE-US-00036 Ex. Product Variant Yield Ir(L277).sub.3 47% Ir(L278).sub.3 55% Ir(L279).sub.3 46% Ir(L280).sub.3 52% Ir(L281).sub.3 23% Ir(L282).sub.3 00 19% Ir(L283).sub.3 01 25% Ir(L284).sub.3 02 27% Ir(L285).sub.3 03 67%
3) Buchwald Coupling on the Iridium Complexes:

(347) 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 the 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 o-xylene or mesitylene, 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 sat. sodium chloride solution and dried over magnesium sulfate. The solid material is filtered off through a Celite bed and rinsed with o-xylene or mesitylene, 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 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.

(348) Synthesis of Ir(L286).sub.3:

(349) ##STR01304##

(350) Use of 14.5 g (10 mmol) of Ir(L1-Br).sub.3 and 12.9 g (40 mmol) of p-biphenyl-o-biphenylamine [1372775-52-4], mesitylene. Yield: 9.8 g (4.7 mmol), 47%; purity: about 99.8% according to HPLC.

(351) The following compounds can be prepared analogously:

(352) TABLE-US-00037 Ex. Product Yield Ir(L287).sub.3 05 49% Ir(L288).sub.3 06 53%
4) Cyanation of the Iridium Complexes:

(353) A mixture of 10 mmol of the brominated complex, 1.3 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 over 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. Hot extraction and sublimation as in 1) variant A. The crude product can alternatively be chromatographed on silica gel with dichloromethane, optionally with addition of ethyl acetate, and then sublimed.

(354) Synthesis of Ir(L289).sub.3:

(355) ##STR01307##

(356) Use of 16.2 g (10 mmol) of Ir(L96-Br).sub.3 and 3.5 g (39 mmol) of copper(I) cyanide. Yield: 7.7 g (5.2 mmol), 52%; purity: about 99.8% according to HPLC.

(357) The following compound can be prepared analogously:

(358) TABLE-US-00038 Ex. Product Yield Ir(L290).sub.3 08 69%
5) Borylation of the Iridium Complexes:

(359) 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 and 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 cyclohexane.

(360) Synthesis of Ir(L1-B).sub.3:

(361) ##STR01309##

(362) Use of 14.5 g (10 mmol) of Ir(L1-Br).sub.3 and 9.1 g (36 mmol) of bis(pinacolato)diborane [73183-34-3], DMSO, 140° C., 6 h, THF, recrystallisation from THF: methanol. Yield: 7.1 g (4.7 mmol), 47%; purity: about 99.7% according to HPLC.

(363) E: Polymers Containing the Metal Complexes:

(364) 1) General Polymerisation Procedure for the Styryl Group as Polymerisable Group

(365) The monomers in the composition indicated are dissolved in toluene at 80° C. in a total concentration of about 1 mol/l. 60 mg of AIBN are subsequently added, and the mixture is stirred at 80° C. for a further 2 h. After cooling to room temperature, the polymer is obtained by precipitation (dropwise addition) in 100 ml of methanol. The precipitate is filtered off with suction and subsequently again dissolved in a little toluene and re-precipitated in methanol, filtered off with suction and dried in vacuo. The reprecipitation process is carried out a further three times.

(366) Monomers:

(367) ##STR01310##
Polymers:

(368) Composition of the polymers, mol %:

(369) TABLE-US-00039 Polymer M1 [%] M2 [%] M3 [%] M4 [%] Ir complex/[%] P1 80 — — — Ir(L283).sub.3/20 P2 60 — 30 — Ir(L283).sub.3/10 P3 50 10 30 — Ir(L283).sub.3/10 P4 50 10 20 10 Ir(L283).sub.3/10 P5 60 — 30 — Ir(L284).sub.3/10
Molecular Weights and Yield of the Polymers According to the Invention

(370) TABLE-US-00040 Polymer Mn [gmol.sup.−1] Mw [gmol.sup.−1] Yield P1 77,000 17,100 53% P2 133,000 50,600 64% P3 127,000 72,000 60% P4 121,000 51,400 57% P5 76,800 23,260 49%
2) General Polymerisation Procedure for the Bromides or Boronic Acid Derivatives as Polymerisable Group, Suzuki Polymerisation
Variant A—Two-Phase Reaction Mixture:

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

(372) Variant B—One-Phase Reaction Mixture:

(373) 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, di-tert-butylphosphine, S-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.

(374) Monomers/End Cappers:

(375) ##STR01311## ##STR01312##
Polymers:

(376) Composition of the Polymers, Mol %:

(377) TABLE-US-00041 Polymer M1 [%] M2 [%] M3 [%] M4 [%] Ir complex/[%] P6 — 30 — 45 Ir(L1-Br).sub.3/20 P7 10 10 — 35 Ir(L96-Br).sub.3/10 P8 50 — 20 45 Ir(L96-Br).sub.3/10 P9 30 30 — 67.5 Ir(L126-Br).sub.3/10
Molecular Weights and Yield of the Polymers According to the Invention

(378) TABLE-US-00042 Polymer Mn [gmol.sup.−1] Polydispersity Yield P6 167,000 4.6 60% P7 153,000 5.1 57% P8 177,000 6.0 63% P9 224,000 3.7 67%
Production of OLEDs
1) Vacuum-Processed Devices:

(379) 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).

(380) The results for various OLEDs are presented in the following examples. Glass plates with structured ITO (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)/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

(381) 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 6.

(382) 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.

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

(384) The compounds according to the invention can be employed, inter alia, as phosphorescent emitter materials in the emission layer in OLEDs. The compounds Ir(Ref).sub.3 are used as comparison in accordance with the prior art. The results for the OLEDs are summarised in Table 2.

(385) TABLE-US-00043 TABLE 1 Structure of the OLEDs HTL2 EBL HBL ETL Ex. Thickness Thickness EML Thickness Thickness Thickness D-Ir(Ref1).sub.3 HTM EBM M1:M4:Ir(Ref1).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(Ref2).sub.3 HTM EBM M1:M3:Ir(Ref2).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(Ref3).sub.3 HTM EBM M1:M4:Ir(Ref3).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(Ref4).sub.3 HTM EBM M1:M4:Ir(Ref4).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(Ref5).sub.3 HTM EBM M1:M4:Ir(Ref5).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(Ref6).sub.3 HTM EBM M1:M4:Ir(Ref6).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(Ref7).sub.3 HTM EBM M1:M4:Ir(Ref7).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(Ref8).sub.3 HTM EBM M1:M4:Ir(Ref8).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(Ref9).sub.3 HTM EBM M1:M4:Ir(Ref9).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(Ref10).sub.3 HTM EBM M1:M4:Ir(Ref10).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%/50%) 25 nm 20 nm D-Ir(L1).sub.3 HTM EBM M1:M4:Ir(L1).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L96).sub.3 HTM EBM M1:M4:Ir(L96).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L96).sub.3-2 HTM EBM M2:M3:Ir(L96).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L167).sub.3 HTM EBM M1:M4:Ir(L96).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%/50%) 25 nm 20 nm D-Ir(L192).sub.3 HTM EBM M1:M4:Ir(L192).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L215).sub.3 HTM EBM M1:M4:Ir(215).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L226).sub.3 HTM EBM M1:M4:Ir(L226).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L227).sub.3 HTM EBM M1:M4:Ir(L227).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L230).sub.3 HTM EBM M1:M4:Ir(L230).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L231).sub.3 HTM EBM M1:M4:Ir(L231).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L234).sub.3 HTM EBM M1:M4:Ir(L234).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L243).sub.3 HTM EBM M1:M4:Ir(L243).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L248).sub.3 HTM EBM M1:M4:Ir(L248).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L252).sub.3 HTM EBM M1:M4:Ir(L252).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L259).sub.3 HTM EBM M1:M4:Ir(L259).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L260).sub.3 HTM EBM M1:M4:Ir(L260).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L263).sub.3 HTM EBM M1:M4:Ir(L263).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L264).sub.3 HTM EBM M1:M4:Ir(L264).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L267).sub.3 HTM EBM M1:M4:Ir(L267).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L268).sub.3 HTM EBM M1:M4:Ir(L268).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L271).sub.3 HTM EBM M1:M4:Ir(L271).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L279).sub.3 HTM EBM M1:M4:Ir(L279).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L284) HTM EBM M1:M4:Ir(L284) HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L3).sub.2 HTM EBM M1:M4:Ir(L3).sub.2(CL1) HBM ETM1:ETM2 (CL1) 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L158).sub.2 HTM EBM M1:M4:Ir(L158).sub.2(CL8) HBM ETM1:ETM2 (CL8) 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L113).sub.2 HTM EBM M1:M4:Ir(L113).sub.2(L109) HBM ETM1:ETM2 (L109) 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm Pt(L3)(CL1) HTM EBM M1:M4:Pt(L3)(CL1) HBM ETM1:ETM2 180 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 25 nm 20 nm Pt(L283) HTM EBM M1:M4:Pt(L283) HBM ETM1:ETM2 230 nm 20 nm (60%:35%:5%) 10 nm (50%:50%) 25 nm 20 nm

(386) TABLE-US-00044 TABLE 2 Results of the vacuum-processed OLEDs 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-Ir(Ref1).sub.3 10.0 4.1 0.16/0.48 1700 D-Ir(Ref2).sub.3 13.2 4.7 0.15/0.31 600 D-Ir(Ref3).sub.3 11.8 4.2 0.16/0.33 1100 D-Ir(Ref4).sub.3 10.3 4.4 0.15/0.24 600 D-Ir(Ref5).sub.3 4.6 4.3 0.16/0.29 — D-Ir(Ref6).sub.3 4.7 4.5 0.15/0.26 — D-Ir(Ref7).sub.3 9.0 4.7 0.15/0.22 200 D-Ir(Ref8).sub.3 6.3 4.7 0.15/0.17 — D-Ir(Ref9).sub.3 10.8 4.5 0.18/0.34 150 D-Ir(Ref10).sub.3 7.9 4.3 0.25/0.61 — D-Ir(L1).sub.3 22.8 4.0 0.15/0.39 1400 D-Ir(L96).sub.3 23.0 4.0 0.14/0.34 1200 D-Ir(L96).sub.3 21.7 4.8 0.14/0.34 1000 D-Ir(L167).sub.3 21.3 4.1 0.15/0.35 1600 D-Ir(L192).sub.3 20.8 4.5 0.15/0.25 900 D-Ir(L215).sub.3 23.7 4.1 0.22/0.71 — D-Ir(L226).sub.3 21.5 4.2 0.25/0.69 36000 D-Ir(L227).sub.3 21.9 3.9 0.29/0.67 — D-Ir(L230).sub.3 9.7 4.3 0.14/0.30 — D-Ir(L231).sub.3 13.8 4.5 0.15/0.40 — D-Ir(L234).sub.3 19.9 4.5 0.14/0.28 600 D-Ir(L243).sub.3 18.7 4.6 0.14/0.24 350 D-Ir(L248).sub.3 19.2 4.6 0.14/0.21 300 D-Ir(L252).sub.3 25.2 4.3 0.23/0.70 — D-Ir(L259).sub.3 22.9 4.2 0.23/0.69 — D-Ir(L260).sub.3 23.2 4.2 0.23/0.70 — D-Ir(L263).sub.3 18.7 4.3 0.15/0.26 600 D-Ir(L264).sub.3 18.4 4.3 0.14/0.34 1400 D-Ir(L267).sub.3 17.3 4.6 0.15/0.33 — D-Ir(L268).sub.3 17.7 4.6 0.15/0.26 — D-Ir(L271).sub.3 19.8 4.8 0.14/0.22 — D-Ir(L279).sub.3 16.7 4.3 0.15/0.22 — D-Ir(L284) 17.0 4.4 0,15/0.24 — D-Ir(L3).sub.2(CL1) 21.8 4.0 0.15/0.38 — D-Ir(L158).sub.2(CL8) 23.1 4.3 0.15/0.25 1200 D-Ir(L113).sub.2(L109) 23.9 4.0 0.14/0.33 1300 D-Ir(I500).sub.3 20.1 4.4 0.16/0.36 500 D-Ir(I511).sub.3 22.7 4.1 0.24/0.65 41000 Pt(L3)(CL1) 17.4 4.6 0.16/0.38 — Pt(L283) 21.4 4.5 0.26/0.63 —
1) Solution-Processed Devices:
A: From Soluble Functional Materials

(387) 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 2004/037887).

(388) 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 5×10.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.

(389) B: From Polymeric Ir Complexes

(390) The production of a polymeric organic light-emitting diode (PLED) has already been described many times in the literature (for example WO 2004/037887).

(391) The substrates are prepared—as described under A: From soluble functional materials—then firstly 20 nm of an interlayer (typically a hole-dominated polymer, here HIL-012 from Merck) and then 65 nm of the polymer layers are applied from toluene solution (concentration of interlayer 5 g/l) under an inert-gas atmosphere (nitrogen or argon). The two layers are dried by heating at 180° C. for at least 10 minutes. The cathode is then applied by vapour deposition from barium (5 nm) and then aluminium (100 nm). 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.

(392) TABLE-US-00045 TABLE 3 Results with solution-processed materials Ir(L).sub.3 or EQE (%) Voltage (V) CIE x/y Ex. Ir polymer 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 D-Ir(L276).sub.3 Ir(L276).sub.3 22.6 4.4 0.16/0.40 D-Ir(L281).sub.3 Ir(L281).sub.3 23.2 4.5 0.15/0.36 D-Ir(L285).sub.3 Ir(L285).sub.3 23.0 4.4 0.15/0.35 D-Ir(L287).sub.3 Ir(L287).sub.3 20.5 4.3 0.22/0.67 D-P1 P1 22.8 4.8 0.15/0.37 D-P5 P5 22.5 4.5 0.15/0.36 D-P6 P6 22.4 4.5 0.16/0.40 D-P7 P7 22.8 4.4 0.15/0.36 D-P9 P9 21.2 4.6 0.15/0.36
2) White-Emitting OLEDs

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

(394) TABLE-US-00046 TABLE 4 Structure of the white OLEDs EML EML EML HTL2 Red Blue Green HBL ETL Ex. Thickness Thickness Thickness Thickness Thickness Thickness D-W1 HTM EBM:Ir-R M1:M3:Ir(L109).sub.3 M3:Ir-G M3 ETM1:ETM2 (97%:3%) (45%:50%:5%) (90%:10%) (50%:50%) 230 nm 9 nm 8 nm 7 nm 10 nm 30 nm

(395) TABLE-US-00047 TABLE 5 Device results CIE x/y EQE (%) Voltage (V) 1000 cd/m.sup.2 LT50 (h) Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 CRI 1000 cd/m.sup.2 D-W1 23.0 6.3 0.45/0.44 3000 80

(396) TABLE-US-00048 TABLE 6 Structural formulae of the materials used HTM EBM M1 M2 M3 M4 = HBM M5 0 M6 Ir-R Ir-G WO2010086089 Ir(Ref-1).sub.3 WO2011157339 Ir(Ref-2).sub.3 WO2011157339 Ir(Ref-3).sub.3 WO2011157339 Ir(Ref-4).sub.3 WO2011157339 Ir(Ref-5).sub.3 WO2011157339 Ir(Ref-6).sub.3 WO2011157339 Ir(Ref-7).sub.3 0 WO2011157339 Ir(Ref-8).sub.3 WO2008/156879 Ir(Ref-9).sub.3 WO2008/156879 Ir(Ref-10).sub.3 ETM1 ETM2