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  formula (1) comprising a moiety M(L).sub.n of formula (2): ##STR00856## wherein M is iridium or platinum; CyC is an aryl or heteroaryl group having 5 to 18 aromatic ring atoms or a fluorene group, each of which is coordinated to M via a carbon atom, each of which is optionally substituted by one or more radicals R, and each of which is connected to CyD via a covalent bond; CyD is a heteroaryl group having 5 to 18 aromatic ring atoms, which is coordinated to M via a neutral nitrogen atom, and which is optionally substituted by one or more radicals R, and which is connected to CyC via a covalent bond; 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).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.1, wherein one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, NR.sup.1, S, or CONR.sup.1, and wherein one or more H atoms is optionally replaced by D, F, Cl, Br, I, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is 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, which is optionally substituted by one or more radicals R.sup.1; 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, 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, or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent CH.sub.2 groups 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, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is 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, which is optionally substituted by one or more radicals R.sup.2; and wherein two or more adjacent radicals R.sup.1 optionally define a mono- or polycyclic, aliphatic ring system with one another; 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, a bidentate ligand which is bonded to M via one carbon atom and one nitrogen atom or via two carbon atoms; n is 1, 2, or 3 when M is iridium and is 1 or 2 when M is platinum; m is 0, 1, or 2 when M is iridium and is 0 or 1 when M is platinum; wherein CyC and CyD are optionally linked to one another via a group selected from the group consisting of C(R.sup.1).sub.2, C(R.sup.1).sub.2—C(R.sup.1).sub.2, NR.sup.1, O, and S; a plurality of ligands L are optionally linked to one another or L may be linked to L′ via a single bond or a divalent or trivalent bridge so as to form a tetradentate or hexadentate ligand system; and CyD contains two adjacent carbon atoms, each of which is substituted by radicals R, where the respective radicals R, together with the C atoms, form a ring of formula (3): ##STR00857## 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 is, identically or differently on each occurrence, C(R.sup.1).sub.2, O, S, NR.sup.3, or C(═O), with the proviso that two heteroatoms in the group -(A).sub.p- are not bonded directly to one another; R.sup.3 is, identically or differently on each occurrence, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent CH.sub.2 groups 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, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, an aryloxy or hetero aryloxy group having 5 to 24 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or an aralkyl or heteroaralkyl group having 5 to 24 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2; wherein two radicals R.sup.3 which are bonded to the same carbon atom optionally define an aliphatic or aromatic ring system with one another so as to form a spiro system; and wherein R.sup.3 optionally defines an aliphatic ring system with an adjacent radical R or R.sup.1; p is, identically or differently on each occurrence, 2 or 3.

2. The compound of claim 1, wherein the CyC is selected from the group consisting of structures of formulae (CyC-1) through (CyC-19), wherein CyC is in each case bonded to CyD at the position denoted by # and coordinated to M at the position denoted by *: ##STR00858## ##STR00859## ##STR00860## and wherein CyD is selected from the group consisting of structures of formulae (CyD-1) through (CyD-4) and (CyD-7) through (CyD-10), wherein the group CyD is in each case bonded to CyC at the position denoted by # and coordinated to M at the position denoted by * ##STR00861## ##STR00862## wherein X is on each occurrence, identically or differently, CR or N; W is on each occurrence, identically or differently, NR, O or S; and two adjacent groups X in CyC and/or in CyD are each CR and, together with the radicals R which are bonded to these carbon atoms, form a group of formula (3).

3. The compound of claim 1, wherein CyC is selected from the group consisting of structures of formulae (CyC-1a) through (CyC-19a), wherein CyC is in each case bonded to CyD at the position denoted by # and coordinated to M at the position denoted by *: ##STR00863## ##STR00864## ##STR00865## and wherein CyD is selected from the group consisting of structures of formulae (CyD-1a) through (CyD-4a) and (CyD-7a) through (CyD-10a), wherein CyD is in each case bonded to CyC at the position denoted by # and coordinated to M at the position denoted by *: ##STR00866## wherein two adjacent radicals R in at least one of the groups CyC and/or CyD, together with the carbon atoms to which they are bonded, form a ring of formula (3).

4. The compound of claim 1, wherein the group of formula (3), when p is 2, is selected from the group consisting of structures of formulae (4-A) and (4-B) and, when p is 3, is selected from the group consisting of structures of formulae (5-A), (5-B), and (5-C): ##STR00867## wherein A is O or NR.sup.3.

5. The compound of claim 4, wherein R.sup.1 in formulae (3), (4-A), (4-B), (5-A), (5-B), and (5-C) is, identically or differently on each occurrence, H, D, or an alkyl group having 1 to 5 C atoms, wherein one or more H atoms are optionally replaced by F and wherein two or more adjacent radicals R.sup.1 optionally define an aliphatic ring system with one another.

6. The compound of claim 1, wherein the compound is selected from the group consisting of compounds of formulae (6) through (11): ##STR00868## wherein V is a single bond or a bridging unit containing 1 to 80 atoms from the third, fourth, fifth, and/or sixth main group or a 3- to 6-membered homo- or heterocycle which covalently bonds the sub-ligands L to one another or covalently bonds L to L′.

7. The compound of claim 2, wherein L′ is a monoanionic bidentate ligand which is bonded to M via a neutral nitrogen atom and a negatively charged carbon atom or via a neutral carbon atom and a negatively charged carbon atom.

8. The compound of claim 7, wherein L′ is a combination of two groups selected from the group consisting of structures of formulae (27) through (50): ##STR00869## ##STR00870## ##STR00871## wherein the two groups are in each case bonded to one another at the position denoted by # and coordinated to M at the position denoted by *; X is on each occurrence, identically or differently, CR or N; and two radicals R which are bonded to two different rings of formulae (27) through (50) optionally define an aromatic ring system with one another.

9. A formulation comprising one or more compounds of claim 1 and at least one further compound.

10. The formulation of claim 9, wherein the at least one further compound is a solvent.

11. An electronic device comprising, in at least one layer, at least one compound of claim 1.

12. The electronic device of claim 11, wherein the 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.

13. The electronic device of claim 12, wherein the electronic device is an organic electroluminescent device and the compound of claim 1 is employed as an emitting compound in one or more emitting layers.

14. The electronic device of claim 13, wherein the emitting layer comprises one or more matrix materials selected from the group consisting of ketones, phosphine oxides, sulfoxides, sulfones, triarylamines, carbazoles, indolocarbazoles, indenocarbazoles, azacarbazoles, bipolar matrix materials, silanes, azaboroles, boronic esters, diazasiloles, diazaphospholes, triazines, zinc complexes, dibenzofurans, and bridged carbazoles.

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.

A: Synthesis of the Synthones S, SP, SH, SB

Example SP1: Pinacolyl 1,1,3,3-Tetramethylindane-5-boronate

(2) Variant 1:

(3) ##STR00063##

A) 5-Bromo-1,1,3,3-tetramethylindane[169695-24-3], SP1-Br

(4) ##STR00064##

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

B) Pinacolyl 1,1,3,3-tetramethylindane-5-boronate, SP1

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

(7) Variant 2:

(8) ##STR00065##

(9) 3.3 g (5 mmol) of bis[(1,2,5,6-η)-1,5-cyclooctadiene]di-μ-methoxydiiridium-(I) [12148-71-9], then 2.7 g (10 mmol) of 4,4′-di-tert-butyl-[2,2′]bipyridinyl [72914-19-3] and then 5.1 g (10 mmol) of bis(pinacolato)diborane are added to 800 ml of n-heptane, and the mixture is stirred at room temperature for 15 min. 127.0 g (500 mmol) of bis(pinacolato)diborane and then 87.2 g (500 mmol) of 1,1,3,3-tetramethylindane [4834-33-7] are subsequently added, and the mixture is warmed at 80° C. for 12 h (TLC check, heptane:ethyl acetate 5:1). After cooling of the reaction mixture, 300 ml of ethyl acetate are added, the mixture is filtered through a silica-gel bed, and the filtrate is evaporated to dryness in vacuo. The crude product is recrystallised twice from acetone (about 800 ml). Yield: 136.6 g (455 mmol), 91%; purity: about 99% according to .sup.1H-NMR.

(10) The following compounds can be prepared analogously:

(11) TABLE-US-00004 Product Starting Boronic acid ester Ex. material Bromide Variant Yield SP2   91324-94-6   SP2-Br   SP2 1 80% SP2   91324-94-6 — 0   SP2 1 95% SP3   142076-41-3   SP3-Br   SP3 1 81% SP4   59508-28-0   SP4-Br   SP4 1 78% SP5   4486-29-7   16499-72-2 SP5-Br   SP5 1 80% SP6 0   35185-96-7   SP6-Br   SP6 1 82% SP7   113710-83-1   SP7-Br   SP7 1 79% SP7   113710-83-1 —   SP7 2 89% SH1   6683-46-1   SH1-Br 27452-17-1 0   SH1 1 74% SH1   6683-46-1 —   2 SH1 92% SB1   4175-52-4   SB1-Br   SB1 1 80% SB1   4175-52-4 —   SB1 2 93% SB2   2716-23-6   SB2-Br 00   SB2 1 81% SB2 01   2716-23-6 — 02   SB2 2 90% SB3 03   60749-53-3 04   SB3-Br 05   SB3 1 74% SB3 06   60749-53-3 — 07   SB3 2 94% SH17 08   853763-39-0 — 09   SH17 2 84% SH18 0   872286-95-8 —   SH18 2 90%

Example SP8: 5,6-Dibromo-1,1,2,2,3,3-hexamethylindane

(12) ##STR00112##

(13) 1.3 g of anhydrous iron(III) chloride and then, dropwise with exclusion of light, a mixture of 64.0 ml (1.25 mol) of bromine and 300 ml of dichloromethane are added to a solution of 101.2 g (500 mmol) of 1,1,2,2,3,3-hexamethylindane [91324-94-6] in 2000 ml of dichloromethane at such a rate that the temperature does not exceed 25° C. If necessary, the mixture is counter-cooled using a cold-water bath. The reaction mixture is stirred at room temperature for a further 16 h, 500 ml of saturated sodium sulfite solution are then slowly added, the aqueous phase is separated off, the organic phase is washed three times with 1000 ml of water each time, dried over sodium sulfate, filtered through a short silica-gel column, and the solvent is then stripped off. Finally, the solid is recrystallised once from a little (about 100 ml) ethanol. Yield: 135.8 g (377 mmol), 75%; purity: about 95% according to .sup.1H-NMR.

(14) The following compounds are prepared analogously:

(15) TABLE-US-00005 Ex. Starting materials Product Yield SP9   113710-83-1   SP9 80% SH2   6683-46-1   184885-74-3 SH2 76% SB4   4175-52-4   SB4 69% SB5   2716-23-6 0   SB5 72% SB6   60749-53-3   SB6 78%

Example SP10: 5,6-Diamino-1,1,2,2,3,3-hexamethylindane

(16) ##STR00123##

A: 6,6-Dinitro-1,1,2,2,3,3-tetramethylindane, SP10a

(17) ##STR00124##

(18) 350 ml of 100% by weight nitric acid are slowly added dropwise to a vigorously stirred mixture, cooled to 0° C., of 101.2 g (500 mmol) of 1,1,2,2,3,3-hexamethylindane [91324-94-6] and 350 ml of 95% by weight sulfuric acid at such a rate that the temperature does not exceed +5° C. The reaction mixture is subsequently allowed to warm slowly to room temperature over 2-3 h and is then poured into a vigorously stirred mixture of 6 kg of ice and 2 kg of water. The pH is adjusted to 8-9 by addition of 40% by weight NaOH, the mixture is extracted three times with 1000 ml of ethyl acetate each time, the combined organic phases are washed twice with 1000 ml of water each time, dried over magnesium sulfate, the ethyl acetate is then removed virtually completely in vacuo until crystallisation commences, and the crystallisation is completed by addition of 500 ml of heptane. The beige crystals obtained in this way are filtered off with suction and dried in vacuo. Yield: 136.2 g (466 mmol), 93%; purity: about 94% according to .sup.1H-NMR, remainder about 4% of 4,6-dinitro-1,1,3,3-tetramethylindane. About 3% of 4,5-dinitro-1,1,3,3-tetramethylindane, S35b, can be isolated from the mother liquor.

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

(19) 136.2 g (466 mmol) of 5,6-dinitro-1,1,2,2,3,3-hexamethylindane, S35a, are hydrogenated at room temperature in 1200 ml of ethanol on 10 g of palladium/carbon at a hydrogen pressure of 3 bar for 24 h. The reaction mixture is filtered twice through a Celite bed, the brown solid obtained after removal of the ethanol is subjected to a bulb-tube distillation (T about 160° C., p about 10.sup.−4 mbar). Yield: 98.5 g (424 mmol), 91%; purity: about 95% according to .sup.1H-NMR.

(20) The following compounds are prepared analogously:

(21) TABLE-US-00006 Ex. Starting materials Product Yield SP11   4834-33-7   SP11 84% SP12   142076-41-3   SP11 76% SH3   6683-46-1 0   SH3 75% SB7   4175-52-4   SB7 72% SB8   2716-23-6   SB8 70% SB9   60749-53-3   SB9 74%

Example SP13: N-[2-(1,1,2,2,3,3-Hexamethylindan-5-yl)ethyl]benzamide

(22) ##STR00137##

A: 1,1,2,2,3,3-Hexamethylindane-5-carboxaldehyde, SP13a

(23) ##STR00138##

(24) 200 ml (500 mmol) of n-BuLi, 2.5 M in n-hexane, are added dropwise to a vigorously stirred solution, cooled to −78° C., of 140.6 g (500 mmol) of 5-bromo-1,1,2,2,3,3-hexamethylindane, SP2-Br, in 1000 ml of THF at such a rate that the temperature does not exceed −55° C. When the addition is complete, the mixture is stirred for a further 30 min., and a mixture of 42.3 ml (550 mmol) of DMF and 50 ml of THF is then allowed to run in with vigorous stirring. The mixture is stirred at −78° C. for a further 1 h, then allowed to warm to room temperature and quenched by addition of 300 ml of saturated ammonium chloride solution. The organic phase is separated off, the THF is removed in vacuo, the residue is taken up in 500 ml of ethyl acetate, washed once with 300 ml of 5% hydrochloric acid, twice with 300 ml of water each time, once with 300 ml of saturated sodium chloride solution, the organic phase is dried over magnesium sulfate, and the solvent is then removed in vacuo. The residue is employed in step B without further purification. Yield: 107.1 g (465 mmol), 93%; purity: about 95% according to .sup.1H-NMR.

(25) The following compounds can be prepared analogously:

(26) TABLE-US-00007 Starting Ex. material Product Yield SP14a   SP3-Br 0   SP14a 91% SH4a   SH1-Br   SH4a 89% SB10a   SB3-Br   SB10a 88%

B: 2-(1,1,2,2,3,3-Hexamethyl-5-Indanyl)ethylamine, SP13b

(27) ##STR00145##

(28) A mixture of 80.6 g (350 mmol) of 1,1,2,2,3,3-hexamethylindane-5-carboxaldehyde, SP13a, 400 ml of nitromethane and 4.6 g (70 mmol) of ammonium acetate, anhydrous, is heated under reflux for 2 h until the starting material has been consumed (TLC check). After cooling, the reaction mixture is poured into 1000 ml of water, extracted three times with 300 ml of dichloromethane each time, the combined organic phases are washed three times with saturated sodium hydrogencarbonate solution, three times with 300 ml of water each time and once with 300 ml of saturated sodium chloride solution, dried over magnesium sulfate, and the solvent is removed in vacuo. The dark oily residue is dissolved in 100 ml of THF and slowly added dropwise with ice-cooling to a solution of 38.0 g (1.0 mol) of lithium aluminium hydride in 1000 ml of THF (care: exothermic reaction?). When the addition is complete, the reaction mixture is allowed to warm to room temperature and is stirred at room temperature for a further 20 h. The reaction mixture is hydrolysed with ice-cooling by slow addition of 500 ml of saturated sodium sulfate solution. The salts are filtered off with suction, rinsed with 500 ml of THF, the THF is removed in vacuo, the residue is taken up in 1000 ml of dichloromethane, the solution is washed three times with 300 ml of water each time, once with 300 ml of saturated sodium chloride solution, dried over magnesium sulfate, and the solvent is then removed in vacuo. The purification is carried out by bulb-tube distillation (p about 10.sup.−4 mbar, T=200° C.). Yield: 67.0 g (273 mmol), 78%; purity: about 95% according to .sup.1H-NMR.

(29) The following compounds can be prepared analogously:

(30) TABLE-US-00008 Starting Ex. material Product Yield SP14b   S14a   S14b 74% SH4b   SH4a   SH4b 70% SB10b 0   SB10a   SB10b 72%

C: N-[2-(1,1,2,2,3,3-Hexamethylindan-5-yl)ethyl]benzamide, SP13

(31) A solution of 14.1 ml (100 mmol) of benzoyl chloride [98-88-4] in 100 ml of dichloromethane is added dropwise with vigorous stirring at 0° C. to a mixture of 24.5 g (100 mmol) of 2-(1,1,2,2,3,3-hexamethyl-5-indanyl)ethylamine, SP13b, 14.1 ml (100 mmol) of triethylamine and 150 ml of dichloromethane at such a rate that the temperature does not exceed 30° C. The mixture is subsequently stirred at room temperature for a further 1 h. The dichloromethane is removed in vacuo, 100 ml of methanol are added to the colourless solid, which is filtered off with suction, washed three times with 50 ml of methanol and dried in vacuo. Yield: 31.1 g (89 mmol), 89%; purity: about 98% according to .sup.1H-NMR.

(32) The following compounds can be prepared analogously:

(33) TABLE-US-00009 Starting Carboxylic Ex. material acid chloride Product Yield SP14   SP14b   6613-441   SP14 74% SP15   SP13b   6613-441   SP15 86% SP16   SP13b   765314- 57-6 0   SP16 88% SP17   SP13b   1710-98-1   SP17 83% SP18   SP13b   14002-51-8   SP18 80% SH4   SH4b   98-88-4   SH4 70% SH5 0   SH4b   1710-98-1   SH5 76% SH6   SH4b   14002-51-8   SH6 73% SH7   SH4b   1005786-37- 7   SH7 74% SH8   SH4b 0   104224-50-2   SH8 72% SH9   SH4b   104224-50-2   SH9 72% SH10   SH4b   100793-48-4   SH10 76% SB10   SB10b   98-88-4 0   SB10 82%

Example SP19: 7-Bromo-1,2,3,4-tetrahydro-1,4-methanonaphthalene-6-carbaldehyde

(34) ##STR00191##

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

(36) TABLE-US-00010 Ex. Starting materials Product Yield SP20   SP8   SP20 68% SP21   SP9   SP21 60% SH11   SH2   SH11 60% SB11   SB4   SB11 55% SB12 00   SB5 01   SB12 50% SB13 02   SB6 03   SB13 53%

Example SP22: 7-Phenylethynyl-1,2,3,4-tetrahydro-1,4-methanonaphthalene-6-carbaldehyde

(37) ##STR00204##

(38) 1.6 g (6 mmol) of triphenylphosphine, 674 mg (3 mmol) of palladium(II) acetate, 571 mg (30 mmol) of copper(I) iodide and 15.3 g (150 mmol) of phenylacetylene [536-74-3] are added consecutively to a solution of 25.1 g (100 mmol) of 7-bromo-1,2,3,4-tetrahydro-1,4-methanonaphthalene-6-carbaldehyde, SP19, in a mixture of 200 ml of DMF and 100 ml of triethylamine, and the mixture is stirred at 65° C. for 4 h. After cooling, the precipitated triethylammonium hydrochloride is filtered off with suction, rinsed with 30 ml of DMF. The filtrate is freed from the solvents in vacuo. The oily residue is taken up in 300 ml of ethyl acetate, the solution is washed five times with 100 ml of water each time and once with 100 ml of saturated sodium chloride solution, and the organic phase is dried over magnesium sulfate. After removal of the ethyl acetate in vacuo, the oily residue is chromatographed on silica gel (n-heptane:ethyl acetate 99:1). Yield: 19.6 g (72 mmol), 72%; purity: about 97% according to .sup.1H-NMR.

(39) The following derivatives can be prepared analogously:

(40) TABLE-US-00011 Bromo- Ex. arylaldeyde Alkyne Product Yield SP23 05   SP20 06   536-74-3 07   SP23 69% SP24 08   SP20 09   25837-46-1 0   S24 69% SP25   SP21   2949-26-0   SP25 70% SH12   SH11   536-74-3   SH12 66% SH13   SH11   188889-51-2   SH13 67% SB14 0   SB11   536-74-3   SB14 61% SB15   SB12   876726-86-2   SB15 63% SB16   SB13   188889-51-2   SB16 73%

Example SB17

(41) ##STR00229##

(42) Procedure analogous to G. Zhang et al., Ad. Synth. & Catal., 2011, 353(2+3), 291. A mixture of 28.4 g (100 mmol) of SB1, 9.4 g (105 mmol) of copper(I) cyanide, 41.5 g (300 mmol) of potassium carbonate, 100 g of glass beads (diameter 3 mm) and 400 ml of DMF and 3.6 ml of water is stirred at 70° C. for 10 h. After cooling, the DMF is substantially removed in vacuo, the residue is diluted with 500 ml of dichloromethane, the salts are filtered off through a Celite bed, the filtrate is washed three times with 200 ml of water and once with 100 ml of saturated sodium chloride solution and then dried over magnesium sulfate. The oily residue which remains after removal of the dichloromethane is distilled in a bulb tube. Yield: 11.5 g (63 mmol), 63%; purity: about 97% according to .sup.1H NMR.

(43) The following compounds can be prepared analogously:

(44) TABLE-US-00012 Ex. Starting material Product Yield SP26 0   SP1   SP26 58% SP27   SP2   SP27 60% SP28   SP7   S28 61% SH14   SH1   SH14 62% SB18   SB2   SB18 65% SB19 0   SB3   SB19 66%

Example SH15: Bis-(1,1,4,4-tetramethyltetrahydronaphth-6-yl) ether

(45) ##STR00242##

(46) Procedure analogous to G. Chen et al., Tetrahedron Letters 2007, 48, 3, 47. A vigorously stirred mixture of 53.5 g (200 mmol) of 6-bromo-1,1,4,4-tetramethyltetrahydronaphthalene, SH1-Br, 212.2 g (800 mmol) of tripotassium phosphate trihydrate, 300 g of glass beads (diameter 3 mm), 449 mg (2 mmol) of palladium(II) acetate, 809 mg (4 mmol) of tri-tert-butylphosphine and 1000 ml of dioxane is heated under reflux for 20 h. After cooling, the salts are filtered off with suction and rinsed with 300 ml of dioxane, the filtrate is evaporated in vacuo, the residue is taken up in 500 ml of ethyl acetate, the solution is washed three times with 300 ml of water each time, once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate, and the ethyl acetate is then removed in vacuo. The residue is purified by bulb-tube distillation (p about 10.sup.−4 mbar, T about 180° C.). Yield: 28.1 g (72 mmol), 72%; purity: about 96% according to .sup.1H-NMR.

Example S1: 27-Di-tert-butyl-9,9′-(6-bromopyridin-2-yl)xanthene, S1

(47) ##STR00243##

(48) 120 ml (300 mmol) of n-BuLi, 2.5 M in n-hexane, are added at room temperature to a solution of 84.7 g (300 mmol) of di(4-tert-butylphenyl) ether [24085-65-2] in 1500 ml of diethyl ether, and the mixture is then stirred under reflux for 60 h. After the reaction mixture has been cooled to −10° C., 82.1 g (240 mmol) of bis(6-bromopyridin-2-yl)methanone are added in portions, and the mixture is then stirred at −10° C. for a further 1.5 h. The reaction mixture is quenched by addition of 30 ml of ethanol, the solvent is removed completely in vacuo in a rotary evaporator, the residue is taken up in 1000 ml of glacial acetic acid, 150 ml of acetic anhydride and then, dropwise, 30 ml of conc. sulfuric acid are added with stirring, and the mixture is stirred at 60° C. for a further 3 h. The solvent is then removed in vacuo, the residue is taken up in 1000 ml of dichloromethane, and the mixture is rendered alkaline by addition of 10% by weight aqueous NaOH with ice-cooling. The organic phase is separated off, washed three times with 500 ml of water each time, dried over magnesium sulfate, the organic phase is evaporated to dryness, and the residue is taken up in 500 ml of methanol, homogenised at elevated temperature and then stirred for a further 12 h, during which the product crystallises. The solid obtained after filtration with suction is dissolved in 1000 ml of dichloromethane, the solution is filtered through a Celite bed, the filtrate is evaporated to dryness, the residue is recrystallised twice from toluene:methanol (1:1) and then dried in vacuo. Yield: 56.3 g (87 mmol), 36%; purity: about 95% according to .sup.1H-NMR.

(49) The following compound can be prepared analogously:

(50) TABLE-US-00013 Ex. Starting material Product Yield SH16   SH15   SH16 30%

B: Synthesis of Ligands LP, LH and LB

Example LP1: 2-(1,1,3,3-Tetramethylindan-5-yl)pyridine, LP1

(51) ##STR00246##

(52) 821 mg (2 mmol) of S-Phos and then 249 mg (1 mmol) of palladium(II) acetate are added to a mixture of 30.0 g (100 mmol) of pinacolyl 1,1,3,3-tetramethylindane-5-boronate, SP-1, 17.4 g (110 mmol) of 2-bromo-pyridine [109-04-6], 46.1 g (200 mmol) of tripotassium phosphate monohydrate, 300 ml of dioxane and 100 ml of water, and the mixture is heated under reflux for 16 h. After cooling, the aqueous phase is separated off, the organic phase is evaporated to dryness, the residue is taken up in 500 ml of ethyl acetate, the organic phase is washed three times with 200 ml of water each time, once with 200 ml of saturated sodium chloride solution, dried over magnesium sulfate, the desiccant is filtered off via a Celite bed, and the filtrate is re-evaporated to dryness. The oil obtained in this way is freed from low-boiling components and non-volatile secondary components by fractional bulb-tube distillation twice. Yield: 15.3 g (61 mmol), 61%; purity: about 99.5% according to .sup.1H-NMR.

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

(54) TABLE-US-00014 Product Ex. Boronic acid ester Bromide Ligand Yield LP2   SP2   54151-74-5 66% LP3 0   SP2   1532-71-4 67% LP4   SP3   23952-31-0 61% LP5   SP4   3430-17-9 63% LP6   SP5 0   23952-31-0 58% LP7   SP7   132118-28-6 59% LH1   SH1   109-04-6 60% LH2   SH1   107351-82-6 0 63% LH3   SH1   1142197-19-0 63% LH4   SH1   23952-31-0 64% LH5   SH1   106203-65-0 61% LH6 0   SH1   54151-74-5 59% LH7   SH1   3430-17-9 60% LH8   SH1   959238-69-8 69% LH9   SH1 0   19493-45-9 63% LH10   SH1   132118-28-6 64% LH11   SH1   19136-36-8 67% LH12   SH1   1438809-78-9 00 60% LH13 01   SH1 02   1251041-55-0 03 62% LH14 04   SH1 2.2 eq. of boronic acid 05   26452-80-2 06 65% LH15 07   SH1 2.2 eq. of boronic acid 08   3430-26-0 09 63% LB1 0   SB1   109-04-6 60% LB2   SB1   107351-82-6 55% LB3   SB1   54151-74-5 58% LB4   SB1 0   1532-71-4 54% LB5   SB1   19493-45-9 50% LB6   SB1   132118-28-6 48% LB7   SB1   959238-69-8 0 57% LB8   SB1   106203-65-0 55% LB9   SB1 2.2 eq. of boronic acid   26452-80-2 48% LB10   SB2   109-04-6 61% LB11 0   SB2   1438809-789-9 60% LB12   SB2   139585-70-9 57% LB13   SB2   19493-45-9 56% LB14   SB2 0   132118-28-6 59% LB15   SB2   106203-65-0 53% LB16   SB3   107351-82-6 62% LB17   SB3   106203-65-0 0 59% LB18   SB3   1532-71-4 57% LB19   SB4   19493-45-9 60% LB20   SB3   132118-28-6 62% LB21 0   SB4 2.2 eq. of boronic acid   3430-26-0 47% LH53   SH17   54151-74-5 45% LH54   SH17   1438809-78-9 48% LH55   SH18 0   54151-74-5 40% LH56   SH18   1438809-78-9 42%

Example LP8: 5,5,7,7-Tetramethyl-3-phenyl-6,7-dihydro-5H-[2]pyridino

(55) ##STR00385##

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

(57) 40 ml (100 mmol) of n-butyllithium, 2.5 M in n-hexane, are added dropwise to a mixture, cooled to −78° C., of 10.5 ml (100 mmol) of bromobenzene and 500 ml of diethyl ether, and the mixture is stirred for a further 30 min. 17.5 g (100 mmol) of 5,5,7,7-tetramethyl-6,7-dihydro-5H-[2]pyridine [1562418-53-4], are then added dropwise, the mixture is allowed to warm to room temperature, stirred for a further 12 h, quenched by addition of 100 ml of water, the organic phase is separated off, dried over magnesium sulfate. After removal of the solvent, the oily residue is chromatographed on silica gel with diethyl ether:n-heptane (3:7, v:v) and subsequently subjected to fractional bulb-tube distillation twice. Yield: 12.1 g (48 mmol), 48%; purity: about 99.5% according to .sup.1H-NMR.

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

(59) TABLE-US-00015 Ex. Pyridine Bromide Ligand Yield LH16 38%

Example LP9: 6,6,7,7,8,8-Hexamethyl-2-phenyl-7,8-dihydro-6H-cyclopenta[g]quinoxaline

(60) ##STR00389##

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

(62) A mixture of 23.2 g (100 mmol) of 1,1,2,2,3,3-hexamethylindane-5,6-diamine, SP10, 13.4 g (100 mmol) of oxophenylacetaldehyde [1074-12-0], 767 mg (3 mmol) of iodine and 75 ml of acetonitrile is stirred at room temperature for 16 h. The precipitated solid is filtered off with suction, washed once with 20 ml of acetonitrile, twice with 75 ml of n-heptane each time and then recrystallised twice from ethanolethyl acetate. Finally, the solid is freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.−4-10.sup.−5 mbar, T about 220° C.). Yield: 22.1 g (67 mmol), 67%; purity: about 99.5% according to .sup.1H-NMR.

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

(64) TABLE-US-00016 Ex. Diamine Diketone Ligand Yield LP10 0 58% LH17 46% LH18 49% LH19 00 01 64% LB22 02 03 04 44% LB23 05 06 07 67% LB24 08 09 0 43% LB25 59%

Example LP11: 5,5,6,6,7,7-Hexamethyl-1,2-diphenyl-1,5,6,7-tetrahydroindeno[5,6-d]imidazole

(65) ##STR00414##

(66) Procedure analogous to D. Zhao et al., Org. Lett., 2011, 13, 24, 6516. A mixture of 36.0 g (100 mmol) of 5,6-dibromo-1,1,2,2,3,3-hexamethylindane SP8, 21.6 g (110 mmol) of N-phenylbenzamidine [1527-91-9], 97.8 g (300 mmol) of caesium carbonate, 100 g of 4 A molecular sieve, 1.2 g (2 mmol) of xantphos, 449 mg (2 mmol) of palladium(II) acetate and 600 ml of o-xylene is heated under reflux with vigorous stirring for 24 h. After cooling, the salts are filtered off with suction via a Celite bed, rinsed with 500 ml of o-xylene, the solvent is removed in vacuo, and the residue is recrystallised three times from cyclohexane/ethyl acetate. Finally, the solid is freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.−4-10.sup.−5 mbar, T about 230° C.). Yield: 28.0 g (71 mmol), 71%; purity: about 99.5% according to .sup.1H-NMR.

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

(68) TABLE-US-00017 1,2-Dihalogen Ex. compound Benzamidine Ligand Yield LH20 41% LH21 0 36% LH22 40% LB26 44%

Example LP12: 1,1,5,6,6,7,7-Heptamethyl-3-phenyl-1,5,6,7-tetrahydroindeno[5,6-d]imidazolium iodide, LP12

(69) ##STR00427##

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

(70) ##STR00428##

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

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

(72) ##STR00429##

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

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

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

(75) The following compounds are prepared analogously:

(76) TABLE-US-00018 Brominated aromatic Yield compound over 3 Ex. 1,2-Diamine Alkyl halide Ligand steps LP13 0 46% LH23 40% LH24 38% LB27 0 37% LB28 39%

Example LP14: 1,4,4,6,6-Pentamethyl-3-phenyl-1,4,5,6-tetrahydro-cyclopentaimidazolium iodide

(77) ##STR00445##

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

(78) ##STR00446##

(79) Preparation analogous to G. Bratulescu, Synthesis, 2009, 14, 2319. An intimate mixture of 1.54 g (10.0 mmol) of 3,3,5,5-tetramethylcyclopentane-1,2-dione [20633-06-1], 4.21 g (3.0 mmol) of urotropin, 7.7 g (10 mmol) of ammonium acetate and 0.3 ml of glacial acetic acid is heated in a temperature-controlled microwave until an internal temperature of about 120° C. has been reached, and is then held at this temperature for about 15 min. After cooling, the mass is added to 150 ml of water, the pH is adjusted to 8 using aqueous ammonia solution (10% by weight) with stirring, the precipitated solid is then filtered off with suction and washed with water. After drying, the product is recrystallised from ethanol/ethyl acetate. Yield: 1.17 g (7.1 mmol), 71%; purity: about 98% according to .sup.1H-NMR.

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

(80) ##STR00447##

(81) Preparation analogous to LP12, B). Use of 1.64 g (10.0 mmol) of 4,4,6,6-tetramethyl-1,4,5,6-tetrahydrocyclopentaimidazole, A), the remaining starting materials and solvents are correspondingly adapted stoichiometrically. Yield: 1.53 g (6.3 mmol), 63%; purity: about 98% according to .sup.1H-NMR.

C) 1,4,4,6,6-Pentamethyl-3-phenyl-1,4,5,6-tetrahydrocyclopenta-imidazolium Iodide

(82) Preparation analogous to LP12, C). Use of 2.4 g (10.0 mmol) of 4,4,6,6-tetramethyl-1-phenyl-1,4,5,6-tetrahydrocyclopentaimidazole, B), the remaining starting materials and solvents are correspondingly adapted stoichiometrically. Yield: 2.26 g (5.9 mmol), 59%; purity: about 99% according to .sup.1H-NMR.

(83) The following compounds are prepared analogously:

(84) TABLE-US-00019 Brominated aromatic compound Yield Ex. 1,2-Dione Alkyl halide Ligand 3 steps LH25 0 28% LB29 33%

Example LP15: 1,1,2,2,3,3-Hexamethyl-5-phenyl-2,3-dihydro-1H-6-azacyclopenta[b]naphthalene

(85) ##STR00454##

(86) 17.0 g (120 mmol) of phosphorus pentoxide are added in portions with vigorous stirring at 90° C. to a solution of 34.8 g (100 mmol) of N-[2-(1,1,2,2,3,3-hexamethylindan-5-yl)ethyl]benzamide, SP13, in 150 ml of o-xylene. 28.0 ml (300 mmol) of phosphoryl chloride are added dropwise to this reaction mixture, which is then stirred under reflux for a further 4 h. The reaction mixture cooled to 80° C. is poured onto 1000 g of ice with vigorous stirring and then rendered alkaline (pH about 12) by addition of solid NaOH. The mixture is extracted three times with 300 ml of toluene each time, the organic phase is washed three times with water, dried over magnesium sulfate, and the solvent is removed in vacuo. The oily residue is dissolved in 200 ml of o-dichlorobenzene, 86.9 g (1 mol) of manganese dioxide are added to the solution, and the mixture is subsequently boiled under reflux on a water separator for 16 h. After cooling, the manganese dioxide is filtered off via a Celite bed, the solid is washed with 500 ml of a mixture of dichloromethane and ethanol (10:1), and the combined filtrates are freed from the solvents in vacuo. The residue is recrystallised from cyclohexane/ethyl acetate and finally freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.−4-10.sup.−5 mbar, T about 230° C.). Yield: 20.1 g (61 mmol), 61%; purity: about 99.5% according to .sup.1H-NMR.

(87) The following compounds can be prepared analogously:

(88) TABLE-US-00020 Ex. Starting material Product Yield LP16 66% LP17 67% LP18 0 65% LH26 63% LH27 60% LH28 63% LH29 48% LH30 0 65% LH31 61% LH32 66% LB30 63%

Example LP19: 7,8,9,10-Tetrahydro-7,10-methano-6-phenylphenanthridine

(89) ##STR00477##

(90) 14.2 g (100 mmol) of boron trifluoride etherate are added dropwise to a vigorously stirred mixture of 46.6 g (500 mmol) of aniline, 58.4 g (550 mmol) of benzaldehyde, 94.2 g (1 mol) of norbornene and 1300 ml of dichloromethane, and the mixture is then heated under reflux for 40 h. After cooling, the reaction mixture is washed twice with 400 ml of water each time, the organic phase is dried over magnesium sulfate, and the dichloromethane is then removed in vacuo. The residue is taken up in 1000 ml of o-dichlorobenzene, 435 g (5 mol) of manganese dioxide are added, and the mixture is heated under reflux on a water separator for 16 h. After cooling, 1000 ml of ethyl acetate are added, the manganese dioxide is filtered off with suction via a Celite bed, the manganese dioxide is rinsed with 1000 ml of ethyl acetate, and the combined filtrates are freed from the solvents in vacuo. The residue is recrystallised twice from cyclohexane and finally freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.−4-10.sup.−5 mbar, T about 230° C.). Yield: 76.0 g (280 mmol), 56%; purity: about 99.5% according to .sup.1H-NMR.

(91) The following compounds can be prepared analogously:

(92) TABLE-US-00021 Ex. Starting material Product Yield LP20 66% LB31 0 27% LB32 27%

Example LP21: 5,8-Methano-5,6,7,8-tetrahydro-3-phenyl-2-aza-anthracene

(93) ##STR00484##

(94) A mixture of 13.6 g (50 mmol) of 7-(3,3-dimethylbut-1-ynyl)-1,2,3,4-tetrahydro-1,4-methanonaphthalene-6-carbaldehyde, SP22, and 500 ml of methanolic ammonia solution (2 M) is stirred at 140° C. for 5 h in an autoclave. After cooling, the methanol is removed in vacuo, the oily residue is chromatographed on silica gel (n-heptane:ethyl acetate 95:5) and finally freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.−4-10.sup.−5 mbar, T about 230° C.). Yield: 5.1 g (17 mmol), 34%; purity: about 99.5% according to .sup.1H-NMR.

(95) The following derivatives can be prepared analogously:

(96) TABLE-US-00022 Ex. Starting material Product Yield LP22 37% LP23 29% LP24 0 30% LH33 27% LH34 29% LB33 28% LB34 26% LB35 00 29%

Example LP25: 1R,4S-Methano-1,2,3,4-tetrahydro-9-phenyl-10-aza-phenanthrene

(97) ##STR00501##

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

(99) The following derivatives can be prepared analogously:

(100) TABLE-US-00023 Ex. Starting material Product Yield LB36 02 03 35%

Example LB37

(101) ##STR00504##

(102) Preparation analogous to M. Ohashi et al., J. Am. Chem. Soc, 2011, 133, 18018.

(103) A mixture of 13.4 g (100 mmol) of 2,3-dimethylenebicyclo[2.2.2]octane [36439-79-9], 5.2 g (50 mmol) of benzonitrile [100-47-0], 1.4 g (5 mmol) of biscyclooctadienenickel(0) [1295-35-8], 5.6 g (20 mmol) of tricyclohexylphosphine [2622-14-2] and 200 ml of o-xylene is heated under gentle reflux for 30 h while a gentle stream of argon is passed in. After cooling, the mixture is filtered through a Celite bed, and the solvent is removed in vacuo. The residue is distilled twice in a bulb tube. Yield: 6.4 g (27 mmol), 54%; purity: about 98% according to .sup.1H NMR.

(104) The following compounds can be prepared analogously:

(105) TABLE-US-00024 Ex. Olefin Nitrile Product Yield LH35 05 06 07 22% LH36 08 09 0 18% LH37 24% LH38 20% LH39 19% LH40 0 17% LH41 20% LH42 22% LB38 0 24%

Example LH43: Tetradentate Ligands

(106) ##STR00532##

(107) A mixture of 71.5 g (100 mmol) of SH16, 61.2 g (230 mmol) of phenyl-boronic acid [24388-23-6], 42.4 g (400 mmol) of sodium carbonate, 1.2 g (1 mmol) of tetrakistriphenylphosphinopalladium(0), 300 ml of toluene, 200 ml of dioxane and 300 ml of water is heated under reflux for 30 h. After cooling, the organic phase is separated off, filtered through a Celite bed, with the Celite being rinsed with 300 ml of toluene, the combined filtrates are washed three times with 300 ml of water each time, dried over magnesium sulfate and then freed from toluene in vacuo. The residue is recrystallised three times from ethanol with addition of a little ethyl acetate and finally freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.−5 mbar, T about 310° C.). Yield: 33.3 g (47 mmol), 47%; purity: about 99.5% according to .sup.1H-NMR.

(108) The following compounds can be prepared analogously:

(109) TABLE-US-00025 Starting Ex. Starting material material Product Yield LH44 46% LH45 42%

Example LH46: Tetradentate Ligands

(110) ##STR00539##

(111) Procedure analogous to C. Cao et al., Synth. Commun. 2012, 42, 380. A mixture of 15.2 g (50 mmol) of LH23 B), and 4.7 g (25 mmol) of 1,2-dibromoethane [106-93-4] is heated at 120° C. for 6 h in an autoclave. After cooling, the solid mass is taken up in 100 ml of tert-butyl methyl ether, homogenised with stirring, the white solid is filtered off, washed twice with 50 ml of tert-butyl methyl ether each time and dried in vacuo. Yield: 15.1 g (19 mmol), 76%; purity: about 98.0% according to .sup.1H-NMR.

(112) The following compounds can be prepared analogously:

(113) TABLE-US-00026 Ex. Imidazole Ligand Yield LH47 0 73%

Example LH48: Hexadentate Ligands

(114) ##STR00542##

(115) A mixture of 51.4 g (100 mmol) of tris(6-bromopyridin-2-yl)methoxy-methane [336158-91-9], 103.7 g (330 mmol) of SH1, 42.4 g (400 mmol) of sodium carbonate, 1.2 g (1 mmol) of tetrakistriphenylphosphinopalladium(0), 500 ml of toluene, 300 ml of dioxane and 500 ml of water is heated under reflux for 36 h. After cooling, the organic phase is separated off, filtered through a Celite bed, with the Celite being rinsed with 400 ml of toluene, the combined filtrates are washed three times with 300 ml of water each time, dried over magnesium sulfate and then freed from toluene in vacuo. The residue is recrystallised three times from isopropanol with addition of a little ethyl acetate and finally freed from low-boiling components and non-volatile secondary components by fractional sublimation (p about 10.sup.−5 mbar, T about 310° C.). Yield: 38.7 g (44 mmol), 44%; purity: about 99.5% according to .sup.1H-NMR.

(116) The following compounds can be prepared analogously:

(117) TABLE-US-00027 Starting Starting Ex. material material Product Yield LH49 47% LH50 40%

Example LH51: Hexadentate Ligands

(118) ##STR00549##

(119) Procedure analogous to LH46, where the 1,2-dibromoethane is replaced by 5.2 g (16.7 mmol) of 1,1,1-tris(bromomethyl)ethane [60111-68-4]. Yield: 14.8 g (12 mmol), 72%; purity: about 99.0% according to .sup.1H-NMR.

(120) Compound LH52 can be prepared analogously:

(121) ##STR00550##

(122) 1,1,1-Tris(bromomethyl)ethane is replaced by 6.1 g (16.7 mmol) of cis,cis-1,2,3-cyclopropanetrimethanol trimethanesulfonate [945230-85-3]. Yield: 14.8 g (11.5 mmol), 69%; purity: about 99.0% according to .sup.1H-NMR.

Example LH1: 2-(5,5,8,8-Tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)pyridine, LP1

(123) ##STR00551##

(124) A mixture of 16.4 g (100 mmol) of 1,1,4,4-tetramethyl-2,3-dimethylene-cyclohexane [153495-32-0], 12.4 g (120 mmol) of 2-ethynylpyridine [1945-84-2] and 50 ml of chlorobenzene is stirred at 120° C. for 16 h. 26.1 g (300 mmol) of activated manganese(II) oxide are then added, and the mixture is stirred at 120° C. for a further 3 h. After cooling, the mixture is diluted with 200 ml of ethyl acetate and filtered through a Celite bed, and the solvent and excess 2-ethynylpyridine are removed in vacuo. The oily residue is distilled twice in a bulb tube (p about 10.sup.−4 mbar, T about 190° C.). Yield: 18.8 g (71 mmol), 71%; purity: about 99.0% according to .sup.1H NMR.

(125) The following compounds can be prepared analogously:

(126) TABLE-US-00028 Starting Starting Ex. material material Product Yield LH57 68% LH7 65% LH58 0 73% LH59 70% LH60 63% LH61 78%

C: Synthesis of the Metal Complexes

(127) 1) Homoleptic tris-facial Iridium complexes of the phenylpyridine, phenylimidazole or phenylbenzimidazole type:

Variant A: Trisacetylacetonatoiridium(III) as Iridium Starting Material

(128) A mixture of 10 mmol of trisacetylacetonatoiridium(III) [15635-87-7] and 40-60 mmol (preferably 40 mmol) of the ligand L, optionally 1-10 g—typically in of an inert high-boiling additive as melting aid or solvent, e.g. hexadecane, m-terphenyl, triphenylene, diphenyl ether, 3-phenoxytoluene, 1,2-, 1,3-, 1,4-bisphenoxybenzene, triphenylphosphine oxide, sulfolane, 18-crown-6, triethylene glckol, glycerol, polyethylene glycols, phenol, 1-naphthol, hydroquinone, etc., 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., preferably for complexes having molecular weights greater than about 1300 g/mol. The sublimation is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 230-400° C., with the sublimation preferably being carried out in the form of a fractional sublimation. Complexes which are readily soluble in organic solvents may alternatively also be chromatographed on silica gel.

(129) If chiral ligands are employed, the derived fac-metal complexes are produced in the form of a diastereomer mixture. The enantiomers Λ,Δ in point group C3 generally have significantly lower solubility in the extractant than the enantiomers in point group C1, which are consequently enriched in the mother liquor. Separation of the C3 diastereomers from the C1 diastereomers is frequently possible by this method. In addition, the diastereomers can also be separated by chromatography. If ligands in point group C1 are employed in enantiomerically pure form, a diastereomer pair Λ,Δ in point group C3 is formed. The diastereomers can be separated by crystallisation or chromatography and thus obtained as enantiomerically pure compounds.

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

(130) 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 tris-acetylacetonatoiridium(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.

Variant C: Sodium [cis,trans-dichloro(bisacetylacetonato)]iridate(III) as Iridium Starting Material

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

(132) TABLE-US-00029 Variant Reaction medium Melting aid Reaction temp. Reaction time Ligand Ir complex Suspension medium Ex. L Diastereomer Extractant Yield Ir(LH1).sub.3 LH1 0 A — — 270° C. 24 h EtOH Ethyl acetate 46% Ir(LH1).sub.3 LH1 C Propylene glycol — RF 100 h — o-Xylene 37% Ir(LH2).sub.3 LH2 A — — 270° C. 24 h EtOH Ethyl acetate 52% Ir(LH3).sub.3 LH3 as for Ir(LH2).sub.3 50% Ir(LH4).sub.3 LH4 A — Hydroquinone 280° C. 40 h EtOH Ethyl acetate  9% Ir(LH5).sub.3 LH5 as for Ir(LH2).sub.3 18% Ir(LH6).sub.3 LH6 as for Ir(LH2).sub.3 43% Ir(LH7).sub.3 LH7 as for Ir(LH2).sub.3 37% Ir(LH8).sub.3 LH8 A — Hydroquinone 280° C. 40 h EtOH Ethyl acetate 24% Ir(LH9).sub.3 LH9 as for Ir(LH2).sub.3 37% Ir(LH10).sub.3 LH10 0 as for Ir(LH4).sub.3 10% Ir(LH11).sub.3 LH11 as for Ir(LH8).sub.3 31% Ir(LH12).sub.3 LH12 as for Ir(LH2).sub.3 35% Ir(LH13).sub.3 LH13 as for Ir(LH2).sub.3 32% Ir(LH14).sub.3 LH14 as for Ir(LH2).sub.3 Chromatography Silica gel n-Heptane:DCM 8:1 40% Ir(LH15).sub.3 LH15 as for Ir(LH2).sub.3 Chromatography Silica gel n-Heptane:DCM 8:1 37% Ir(LH16).sub.3 LH16 as for Ir(LH2).sub.3 39% Ir(LH20).sub.3 LH20 A — — 280° C. 30 h EtOH Toluene 40% Ir(LH21).sub.3 LH21 as for Ir(LH20).sub.3 34% Ir(LH22).sub.3 LH22 as for Ir(LH20).sub.3 30% Ir(LH26).sub.3 LH26 0 as for Ir(LH2).sub.3 41% Ir(LH27).sub.3 LH27 as for Ir(LH2).sub.3 43% Ir(LH28).sub.3 LH28 as for Ir(LH2).sub.3 42% Ir(LH29).sub.3 LH29 A — — 280° C. 30 h Acetone Toluene 28% Ir(LH30).sub.3 LH30 as for Ir(LH2).sub.3 Chromatography Silica gel n-Heptane:DCM 8:1 30% Ir(LH31).sub.3 LH31 as for Ir(LH2).sub.3 36% Ir(LH32).sub.3 LH32 as for Ir(LH2).sub.3 Chromatography Silica gel n-Heptane:DCM 8:1 35% Ir(LH33).sub.3 LH33 as for Ir(LH2).sub.3 41% Ir(LH34).sub.3 LH34 as for Ir(LH2).sub.3 40% Ir(LH35).sub.3 LH35 as for Ir(LH2).sub.3 40% Ir(LH36).sub.3 LH36 00 as for Ir(LH2).sub.3 28% Ir(LH37).sub.3 LH37 01 as for Ir(LH2).sub.3 40% Ir(LH38).sub.3 LH38 02 as for Ir(LH2).sub.3 44% Ir(LH39).sub.3 LH39 03 as for Ir(LH2).sub.3 38% Ir(LH40).sub.3 LH40 04 A — Hydroquinone 280° C. 35 h Toluene Ethyl acetate 30% Ir(LH41).sub.3 LH41 05 as for Ir(LH2).sub.3 Chromatography Silica gel Toluene 42% Ir(LH42).sub.3 LH42 06 as for Ir(LH2).sub.3 Chromatography Silica gel Toluene 39% Ir(LH53).sub.3 LH53 07 A — — 270° C. 24 h EtOH Acetonitrile 38% Ir(LH54).sub.3 LH54 08 as for Ir(L53).sub.3 44% Ir(LH55).sub.3 LH55 09 as for Ir(LH2).sub.3 Chromatography Silica gel Toluene 33% Ir(LH56).sub.3 LH56 0 as for Ir(LH2).sub.3 Chromatography Silica gel Toluene 37% Ir(LH57).sub.3 LH57 as for Ir(L53).sub.3 46% Ir(LH58).sub.3 LH58 as for Ir(L53).sub.3 43% Ir(LH59).sub.3 LH59 as for Ir(L53).sub.3 37% Ir(LH60).sub.3 LH60 as for Ir(L53).sub.3 41% Ir(LH61).sub.3 LH61 as for Ir(L2).sub.3 47%
2) Homoleptic Iridium Complexes of the Arduengo Carbene Type:

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

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

(135) TABLE-US-00030 Ligand Ir complex Ex. L Diastereomer Yield fac-Ir(LH23).sub.3 mer-Ir(LH23).sub.3 LH23 35% 10% fac-Ir(LH24).sub.3 mer-Ir(LH24).sub.3 LH24 37% 12% fac-Ir(LH25).sub.3 LH25 33% fac-Ir(LB29).sub.3 LB29 29%
3) Iridium Complexes of the [Ir(L).sub.2Cl].sub.2 Type
Variant A:

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

(137) Variant B:

(138) A mixture of 10 mmol of sodium bisacetylacetonatodichloroiridate(III) [770720-50-8], 24 mmol of ligand L and a glass-clad magnetic stirrer bar are melted into a thick-walled 50 ml glass ampoule in vacuo (10.sup.−5 mbar). The ampoule is heated at the temperature indicated for the time indicated, during which the molten mixture is stirred with the aid of a magnetic stirrer. After 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 dichloromethane, acetone, ethyl acetate, toluene, etc.) and mechanically digested at the same time. The fine suspension is decanted off from the glass beads, the solid [Ir(L).sub.2Cl].sub.2 which still contains about 2 eq. of NaCl, referred to below as the crude chloro dimer) is filtered off with suction and dried in vacuo. The crude chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 obtained in this way is reacted further without purification.

(139) TABLE-US-00031 Ir complex Variant Ligand Temp./time Ex. L Diastereomer Yield [Ir(LP1).sub.2Cl].sub.2 L1 0 76% [Ir(LP2).sub.2Cl].sub.2 L2 Ir[(LP2)Cl].sub.2 81% A [Ir(LH1).sub.2Cl].sub.2 LH1 76% [Ir(LH2).sub.2Cl].sub.2 LH2 [Ir(LH2).sub.2Cl].sub.2 80% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH3).sub.2Cl].sub.2 LH3 [Ir(LH3).sub.2Cl].sub.2 78% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH4).sub.2Cl].sub.2 LH4 [Ir(LH4).sub.2Cl].sub.2 81% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH5).sub.2Cl].sub.2 LH5 [Ir(LH5).sub.2Cl].sub.2 80% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH6).sub.2Cl].sub.2 LH6 [Ir(LH6).sub.2Cl].sub.2 75% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH7).sub.2Cl].sub.2 LH7 [Ir(LH7).sub.2Cl].sub.2 77% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH9).sub.2Cl].sub.2 LH9 [Ir(LH9).sub.2Cl].sub.2 81% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH10).sub.2Cl].sub.2 LH10 [Ir(LH10).sub.2Cl].sub.2 80% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH12).sub.2Cl].sub.2 LH12 [Ir(LH12).sub.2Cl].sub.2 76% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH14).sub.2Cl].sub.2 LH14 [Ir(LH14).sub.2Cl].sub.2 78% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH15).sub.2Cl].sub.2 LH15 [Ir(LH15).sub.2Cl].sub.2 78% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH16).sub.2Cl].sub.2 LH16 [Ir(LH16).sub.2Cl].sub.2 79% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH17).sub.2Cl].sub.2 LH17 [Ir(LH17).sub.2Cl].sub.2 46% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH18).sub.2Cl].sub.2 LH18 [Ir(LH18).sub.2Cl].sub.2 38% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH19).sub.2Cl].sub.2 LH19 [Ir(LH19).sub.2Cl].sub.2 40% as for [Ir(LH1).sub.2Cl].sub.2 [Ir(LH20).sub.2Cl].sub.2 LH20 84% [Ir(LH21).sub.2Cl].sub.2 LH21 [Ir(LH21).sub.2Cl].sub.2 86% as for [Ir(LH20).sub.2Cl].sub.2 [Ir(LH22).sub.2Cl].sub.2 LH22 [Ir(LH22).sub.2Cl].sub.2 83% as for [Ir(LH20).sub.2Cl].sub.2 [Ir(LH26).sub.2Cl].sub.2 LH26 85% [Ir(LH27).sub.2Cl].sub.2 LH27 [Ir(LH27).sub.2Cl].sub.2 85% as for [Ir(LH26).sub.2Cl].sub.2 [Ir(LH28).sub.2Cl].sub.2 LH28 [Ir(LH28).sub.2Cl].sub.2 83% as for [Ir(LH26).sub.2Cl].sub.2 [Ir(LH29).sub.2Cl].sub.2 LH29 [Ir(LH29).sub.2Cl].sub.2 67% as for [Ir(LH26).sub.2Cl].sub.2 [Ir(LH30).sub.2Cl].sub.2 LH30 [Ir(LH30).sub.2Cl].sub.2 83% as for [Ir(LH26).sub.2Cl].sub.2 [Ir(LH31).sub.2Cl].sub.2 LH31 [Ir(LH31).sub.2Cl].sub.2 85% as for [Ir(LH26).sub.2Cl].sub.2 [Ir(LH32).sub.2Cl].sub.2 LH32 [Ir(LH32).sub.2Cl].sub.2 86% as for [Ir(LH26).sub.2Cl].sub.2 [Ir(LH33).sub.2Cl].sub.2 LH33 [Ir(LH32).sub.2Cl].sub.2 86% B 260°C./30 h [Ir(LH34).sub.2Cl].sub.2 LH34 [Ir(LH34).sub.2Cl].sub.2 88% as for [Ir(LH33).sub.2Cl].sub.2 [Ir(LH35).sub.2Cl].sub.2 LH35 86% [Ir(LH36).sub.2Cl].sub.2 LH36 [Ir(LH36).sub.2Cl].sub.2 90% as for [Ir(LH35).sub.2Cl].sub.2 [Ir(LH37).sub.2Cl].sub.2 LH37 [Ir(LH37).sub.2Cl].sub.2 88% as for [Ir(LH35).sub.2Cl].sub.2 [Ir(LH38).sub.2Cl].sub.2 LH38 [Ir(LH38).sub.2Cl].sub.2 89% as for [Ir(LH35).sub.2Cl].sub.2 [Ir(LH39).sub.2Cl].sub.2 LH39 [Ir(LH39).sub.2Cl].sub.2 87% as for [Ir(LH35).sub.2Cl].sub.2 [Ir(LH40).sub.2Cl].sub.2 LH40 [Ir(LH40).sub.2Cl].sub.2 63% B 265° C./35 h [Ir(LH41).sub.2Cl].sub.2 LH41 [Ir(LH41).sub.2Cl].sub.2 89% as for [Ir(LH35).sub.2Cl].sub.2 [Ir(LH42).sub.2Cl].sub.2 LH42 [Ir(LH42).sub.2Cl].sub.2 89% as for [Ir(LH35).sub.2Cl].sub.2 [Ir(LB1).sub.2Cl].sub.2 LB1 76% [Ir(LB2).sub.2Cl].sub.2 LB2 76% [Ir(LB5).sub.2Cl].sub.2 LB5 [Ir(L85).sub.2Cl].sub.2 79% as for [Ir(LB1).sub.2Cl].sub.2 [Ir(LB9).sub.2Cl].sub.2 LB9 [Ir(LB9).sub.2Cl].sub.2 81% as for [Ir(LB2).sub.2Cl].sub.2 [Ir(LB10).sub.2Cl].sub.2 LB10 [Ir(LB10).sub.2Cl].sub.2 76% as for [Ir(LB1).sub.2Cl].sub.2 [Ir(LB16).sub.2Cl].sub.2 LB16 [Ir(LB16).sub.2Cl].sub.2 82% as for [Ir(LB2).sub.2Cl].sub.2 [Ir(LB26).sub.2Cl].sub.2 LB26 75% [Ir(LB30).sub.2Cl].sub.2 LB30 83% [Ir(LB31).sub.2Cl].sub.2 LB31 81% [Ir(LB33).sub.2Cl].sub.2 LB33 0 88% [Ir(LB36).sub.2Cl].sub.2 LB36 53% [Ir(LB37).sub.2Cl].sub.2 LB37 88% [Ir(LB38).sub.2Cl].sub.2 LH42 [Ir(LB38).sub.2Cl].sub.2 87% as for [Ir(LH35).sub.2Cl].sub.2
4) Iridium Complexes of the [Ir(L).sub.2(HOMe).sub.2]OTf Type

(140) 5 ml of methanol and then 10 mmol of silver(I) trifluoromethanesulfonate [2923-28-6] are added to a suspension of 5 mmol of the chloro dimer [Ir(L).sub.2Cl].sub.2 in 150 ml of dichloromethane, and the mixture is stirred at room temperature for 18 h. The precipitated silver(I) chloride is filtered off with suction via a Celite bed, the filtrate is evaporated to dryness, the yellow residue is taken up in 30 ml of toluene or cyclohexane, the solid is filtered off, washed with n-heptane and dried in vacuo. The product of the formula [Ir(L).sub.2(HOMe).sub.2]OTf obtained in this way is reacted further without purification.

(141) TABLE-US-00032 Ex. [Ir(L).sub.2Cl].sub.2 [Ir(L).sub.2(HOMe).sub.2]OTf Yield [Ir(LP1).sub.2(HOMe).sub.2]OTf Ir[(LP1)Cl].sub.2 81% [Ir(LP2).sub.2(HOMe).sub.2]OTf [Ir(LP2).sub.2Cl].sub.2 [Ir(LP2).sub.2(HOMe).sub.2]OTf 79% [Ir(LH1).sub.2(HOMe).sub.2]OTf [Ir(LH1).sub.2Cl].sub.2 [Ir(LH2).sub.2(HOMe).sub.2]OTf [Ir(LH2).sub.2Cl].sub.2 [Ir(LH2).sub.2(HOMe).sub.2]OTf 80% [Ir(LH3).sub.2(HOMe).sub.2]OTf [Ir(LH3).sub.2Cl].sub.2 [Ir(LH3).sub.2(HOMe).sub.2]OTf 78% [Ir(LH4).sub.2(HOMe).sub.2]OTf [Ir(LH4).sub.2Cl].sub.2 [Ir(LH4).sub.2(HOMe).sub.2]OTf 81% [Ir(LH5).sub.2(HOMe).sub.2]OTf [Ir(LH5).sub.2Cl].sub.2 [Ir(LH5).sub.2(HOMe).sub.2]OTf 83% [Ir(LH6).sub.2(HOMe).sub.2]OTf [Ir(LH6).sub.2Cl].sub.2 [Ir(LH6).sub.2(HOMe).sub.2]OTf 80% [Ir(LH7).sub.2(HOMe).sub.2]OTf [Ir(LH7).sub.2Cl].sub.2 [Ir(LH7).sub.2(HOMe).sub.2]OTf 81% [Ir(LH9).sub.2(HOMe).sub.2]OTf [Ir(LH9).sub.2Cl].sub.2 [Ir(LH9).sub.2(HOMe).sub.2]OTf 81% [Ir(LH10).sub.2(HOMe).sub.2]OTf [Ir(LH10).sub.2Cl].sub.2 [Ir(LH10).sub.2(HOMe).sub.2]OTf 86% [Ir(LH12).sub.2(HOMe).sub.2]OTf [Ir(LH12).sub.2Cl].sub.2 [Ir(LH12).sub.2(HOMe).sub.2]OTf 79% [Ir(LH14).sub.2(HOMe).sub.2]OTf [Ir(LH14).sub.2Cl].sub.2 [Ir(LH14).sub.2(HOMe).sub.2]OTf 80% [Ir(LH15).sub.2(HOMe).sub.2]OTf [Ir(LH15).sub.2Cl].sub.2 [Ir(LH15).sub.2(HOMe).sub.2]OTf 83% [Ir(LH16).sub.2(HOMe).sub.2]OTf [Ir(LH16).sub.2Cl].sub.2 [Ir(LH16).sub.2(HOMe).sub.2]OTf 78% [Ir(LH17).sub.2(HOMe).sub.2]OTf [Ir(LH17).sub.2Cl].sub.2 [Ir(LH17).sub.2(HOMe).sub.2]OTf 80% [Ir(LH18).sub.2(HOMe).sub.2]OTf [Ir(LH18).sub.2Cl].sub.2 [Ir(LH18).sub.2(HOMe).sub.2]OTf 82% [Ir(LH19).sub.2(HOMe).sub.2]OTf [Ir(LH19).sub.2Cl].sub.2 [Ir(LH19).sub.2(HOMe).sub.2]OTf 80% [Ir(LH20).sub.2(HOMe).sub.2]OTf [Ir(LH20).sub.2Cl].sub.2 [Ir(LH20).sub.2(HOMe).sub.2]OTf 85% [Ir(LH21).sub.2(HOMe).sub.2]OTf [Ir(LH21).sub.2Cl].sub.2 [Ir(LH21).sub.2(HOMe).sub.2]OTf 86% [Ir(LH22).sub.2(HOMe).sub.2]OTf [Ir(LH22).sub.2Cl].sub.2 [Ir(LH22).sub.2(HOMe).sub.2]OTf 80% [Ir(LH26).sub.2(HOMe).sub.2]OTf [Ir(LH26).sub.2Cl].sub.2 [Ir(LH26).sub.2(HOMe).sub.2]OTf 85% [Ir(LH27).sub.2(HOMe).sub.2]OTf [Ir(LH27).sub.2Cl].sub.2 [Ir(LH27).sub.2(HOMe).sub.2]OTf 84% [Ir(LH28).sub.2(HOMe).sub.2]OTf [Ir(LH28).sub.2Cl].sub.2 [Ir(LH28).sub.2(HOMe).sub.2]OTf 82% [Ir(LH29).sub.2(HOMe).sub.2]OTf [Ir(LH29).sub.2Cl].sub.2 [Ir(LH29).sub.2(HOMe).sub.2]OTf 85% [Ir(LH30).sub.2(HOMe).sub.2]OTf [Ir(LH30).sub.2Cl].sub.2 [Ir(LH30).sub.2(HOMe).sub.2]OTf 84% [Ir(LH31).sub.2(HOMe).sub.2]OTf [Ir(LH31).sub.2Cl].sub.2 [Ir(LH31).sub.2(HOMe).sub.2]OTf 79% [Ir(LH32).sub.2(HOMe).sub.2]OTf [Ir(LH32).sub.2Cl].sub.2 [Ir(LH32).sub.2(HOMe).sub.2]OTf 80% [Ir(LH33).sub.2(HOMe).sub.2]OTf [Ir(LH33).sub.2Cl].sub.2 [Ir(LH33).sub.2(HOMe).sub.2]OTf 82% [Ir(LH34).sub.2(HOMe).sub.2]OTf [Ir(LH34).sub.2Cl].sub.2 [Ir(LH34).sub.2(HOMe).sub.2]OTf 83% [Ir(LH35).sub.2(HOMe).sub.2]OTf [Ir(LH35).sub.2Cl].sub.2 [Ir(LH35).sub.2(HOMe).sub.2]OTf 85% [Ir(LH36).sub.2(HOMe).sub.2]OTf [Ir(LH36).sub.2Cl].sub.2 [Ir(LH36).sub.2(HOMe).sub.2]OTf 81% [Ir(LH37).sub.2(HOMe).sub.2]OTf [Ir(LH37).sub.2Cl].sub.2 [Ir(LH37).sub.2(HOMe).sub.2]OTf 80% [Ir(LH38).sub.2(HOMe).sub.2]OTf [Ir(LH38).sub.2Cl].sub.2 [Ir(LH38).sub.2(HOMe).sub.2]OTf 85% [Ir(LH39).sub.2(HOMe).sub.2]OTf [Ir(LH39).sub.2Cl].sub.2 [Ir(LH39).sub.2(HOMe).sub.2]OTf 80% [Ir(LH40).sub.2(HOMe).sub.2]OTf [Ir(LH40).sub.2Cl].sub.2 [Ir(LH40).sub.2(HOMe).sub.2]OTf 84% [Ir(LH41).sub.2(HOMe).sub.2]OTf [Ir(LH41).sub.2Cl].sub.2 [Ir(LH41).sub.2(HOMe).sub.2]OTf 84% [Ir(LH42).sub.2(HOMe).sub.2]OTf [Ir(LH42).sub.2Cl].sub.2 [Ir(LH42).sub.2(HOMe).sub.2]OTf 86% [Ir(LB1).sub.2(HOMe).sub.2]OTf [Ir(LB1).sub.2Cl].sub.2 82% [Ir(LB2).sub.2(HOMe).sub.2]OTf [Ir(LB2).sub.2Cl].sub.2 [Ir(LB2).sub.2(HOMe).sub.2]OTf 75% [Ir(LB5).sub.2(HOMe).sub.2]OTf [Ir(LB5).sub.2Cl].sub.2 [Ir(LB5).sub.2(HOMe).sub.2]OTf 78% [Ir(LB9).sub.2(HOMe).sub.2]OTf [Ir(LB9).sub.2Cl].sub.2 [Ir(LB9).sub.2(HOMe).sub.2]OTf 79% [Ir(LB10).sub.2(HOMe).sub.2]OTf [Ir(LB10).sub.2Cl].sub.2 [Ir(LB10).sub.2(HOMe).sub.2]OTf 80% [Ir(LB16).sub.2(HOMe).sub.2]OTf [Ir(LB16).sub.2Cl].sub.2 [Ir(LB16).sub.2(HOMe).sub.2]OTf 78% [Ir(LB26).sub.2(HOMe).sub.2]OTf [Ir(LB26).sub.2Cl].sub.2 [Ir(LB26).sub.2(HOMe).sub.2]OTf 78% [Ir(LB30).sub.2(HOMe).sub.2]OTf [Ir(LB30).sub.2Cl].sub.2 [Ir(LB30).sub.2(HOMe).sub.2]OTf 82% [Ir(LB31).sub.2(HOMe).sub.2]OTf [Ir(LB31).sub.2Cl].sub.2 [Ir(LB31).sub.2(HOMe).sub.2]OTf 82% [Ir(LB33).sub.2(HOMe).sub.2]OTf [Ir(LB33).sub.2Cl].sub.2 [Ir(LB33).sub.2(HOMe).sub.2]OTf 76% [Ir(LB36).sub.2(HOMe).sub.2]OTf [Ir(LB36).sub.2Cl].sub.2 [Ir(LB36).sub.2(HOMe).sub.2]OTf 75% [Ir(LB37).sub.2(HOMe).sub.2]OTf [Ir(LB37).sub.2Cl].sub.2 [Ir(LB37).sub.2(HOMe).sub.2]OTf 77% [Ir(LB38).sub.2(HOMe).sub.2]OTf [Ir(LB38).sub.2Cl].sub.2 [Ir(LB38).sub.2(HOMe).sub.2]OTf 74%
5) Heteroleptic Iridium Complexes of the Phenylpyridine, Phenylimidazole or Phenylbenzimidazole Type:

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

(143) TABLE-US-00033 [Ir(L).sub.2(HOMe).sub.2]OTf Ligand Ir complex Ex. L Diastereomer Yield Ir500 1215692-14-0 LH1 44% Ir501 1215692-14-0 LH2 43% Ir502 1215692-14-0 LH3 45% Ir503 1215692-29-7 LH4 27% Ir504 1215692-14-0 LH5 0 38% Ir505 1215692-14-0 LH6 50% Ir506 1215692-14-0 LH7 48% Ir507 1215692-14-0 LH8 24% IR508 1215692-14-0 LH9 42% Ir509 1215692-14-0 LH10 23% Ir510 1215692-14-0 LH11 26% Ir511 1215692-29-7 LH12 44% Ir512 1215692-29-7 LH13 46% Ir513 1215692-14-0 LH14 43% Ir514 1215692-14-0 LH15 0 52% Ir515 1215692-14-0 LH16 40% Ir516 1215692-14-0 LH17 23% Ir517 1215692-14-0 LH18 21% Ir518 1215692-14-0 LH19 25% Ir519 1215692-14-0 LH20 25% Ir520 1215692-14-0 LH26 45% Ir521 1215692-14-0 LH27 41% Ir522 1215692-14-0 LH30 38% Ir523 1215692-14-0 LH31 43% Ir524 1215692-14-0 LH33 0 43% Ir525 1215692-14-0 LH34 43% Ir526 1215692-14-0 LH35 43% Ir527 1215692-14-0 LH36 43% Ir528 1215692-14-0 LH37 43% Ir529 1215692-14-0 LH41 43% Ir530 1215692-14-0 LH42 43% Ir531 1215692-14-0 LB38 43% Ir532 [Ir(LP1).sub.2(HOMe).sub.2]OTf LH1 46% Ir533 [Ir(LP2).sub.2(HOMe).sub.2]OTf LH2 44% Ir534 [Ir(LH1).sub.2(HOMe).sub.2]OTf 1008-89-56 0 46% Ir535 [Ir(LH2).sub.2(HOMe).sub.2]OTf 1008-89-56 50% Ir536 [Ir(LH3).sub.2(HOMe).sub.2]OTf 1008-89-56 43% Ir537 [Ir(LH6).sub.2(HOMe).sub.2]OTf 10273-90-2 45% Ir538 [Ir(LH7).sub.2(HOMe).sub.2]OTf 10273-90-2 38% Ir539 [Ir(LH9).sub.2(HOMe).sub.2]OTf 458541-39-4 46% Ir540 [Ir(LH12).sub.2(HOMe).sub.2]OTf 1008-89-56 45% Ir541 [Ir(LH14).sub.2(HOMe).sub.2]OTf 1008-89-56 40% Ir542 [Ir(LH15).sub.2(HOMe).sub.2]OTf 1008-89-56 40% Ir543 [Ir(LH16).sub.2(HOMe).sub.2]OTf LH1 42% Ir544 [Ir(LH20).sub.2(HOMe).sub.2]OTf 340026-65-5 0 20% Ir545 [Ir(LH21).sub.2(HOMe).sub.2]OTf 1008-89-56 26% Ir546 [Ir(LH22).sub.2(HOMe).sub.2]OTf 4350-51-0 29% Ir547 [Ir(LH26).sub.2(HOMe).sub.2]OTf 1008-89-56 45% Ir548 [Ir(LH27).sub.2(HOMe).sub.2]OTf 37993-76-3 43% Ir549 [Ir(LH28).sub.2(HOMe).sub.2]OTf 37993-76-3 43% Ir550 [Ir(LH29).sub.2(HOMe).sub.2]OTf 230-27-3 21% Ir551 [Ir(LH30).sub.2(HOMe).sub.2]OTf LP2 38% Ir552 [Ir(LH31).sub.2(HOMe).sub.2]OTf LB18 36% Ir553 [Ir(LH32).sub.2(HOMe).sub.2]OTf LB19 39% Ir554 [Ir(LH33).sub.2(HOMe).sub.2]OTf 1008-89-56 0 48% Ir555 [Ir(LH34).sub.2(HOMe).sub.2]OTf LH33 45% Ir556 [Ir(LH35).sub.2(HOMe).sub.2]OTf 1008-89-56 47% Ir557 [Ir(LH36).sub.2(HOMe).sub.2]OTf LH1 36% Ir558 [Ir(LH37).sub.2(HOMe).sub.2]OTf 26274-35-1 41% Ir559 [Ir(LH)38.sub.2(HOMe).sub.2]OTf LB37 45% Ir560 [Ir(LH39).sub.2(HOMe).sub.2]OTf LH6 42% Ir561 [Ir(LH40).sub.2(HOMe).sub.2]OTf 4350-51-0 31% Ir562 [Ir(LH41).sub.2(HOMe).sub.2]OTf 1008-89-56 46% Ir563 [Ir(LH42).sub.2(HOMe).sub.2]OTf 1008-89-56 45% Ir564 [Ir(LB1).sub.2(HOMe).sub.2]OTf LH1 00 44% Ir565 [Ir(LB2).sub.2(HOMe).sub.2]OTf LH38 01 39% Ir566 [Ir(LB3).sub.2(HOMe).sub.2]OTf LH35 02 40% Ir567 [Ir(LB10).sub.2(HOMe).sub.2]OTf LH35 03 41% Ir568 [Ir(LB16).sub.2(HOMe).sub.2]OTf LH38 04 39% Ir569 [Ir(LB33).sub.2(HOMe).sub.2]OTf LH1 05 40% Ir570 [Ir(LB37).sub.2(HOMe).sub.2]OTf LH35 06 45% Ir571 [Ir(LB38).sub.2(HOMe).sub.2]OTf 1008-89-56 07 47%
6) Heteroleptic Tris-Facial Iridium Complexes Containing Ligands of the Arduengo Carbene Type:

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

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

(146) TABLE-US-00034 [Ir(L).sub.2Cl].sub.2 Ir complex Ex. Ligand L Diastereomer Yield Ir572 [Ir(PPy).sub.2Cl].sub.2 603109-48-4 LH23 08 43% Ir573 [Ir(LH20).sub.2Cl].sub.2 LH24 09 45%
7) Platinum Complexes of Tetradentate Ligands:

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

(148) TABLE-US-00035 Ligand Ex. L Pt complex Extractant Yield Pt(LH43) LH43 0 Toluene 40% Pt(LH44) LH44 Pt(LH44) Toluene 19% Pt(LH45) LH45 Pt(LH45) Cyclohexane 37%
10) Platinum Complexes of Tetradentate Ligands of the Arduengo Carbene Type:

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

(150) TABLE-US-00036 Ex. Ligand Pt complex Yield Pt(LH46) LH46 25% Pt(LH47) LH47 Pt(LH47) 28%
11) Iridium Complexes of Hexadentate Ligands:

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

(152) TABLE-US-00037 Ex. Ligand Ir complex Yield Ir(LH48) LH48 21% Ir(LH49) LH49 Ir(LH49) 22% Ir(LH50) LH50 Ir(LH50) 19%
12) Iridium Complexes of Hexadentate Ligands of the Arduengo Carbene Type:

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

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

(155) TABLE-US-00038 Ex. Ligand Ir complex Yield Ir(LH51) LH51 23% Ir(LH52) LH52 Ir(LH52) 17%
Derivatisation of the Metal Complexes
1) Halogenation of the Fac-Iridium Complexes:

(156) A×10.5 mmol of N-halosuccinimide (halogen: Cl, 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 500 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 methanol, the solid is filtered off with suction, washed three times with 30 ml of methanol and then dried in vacuo, giving the fac-iridium complexes which are brominated in the para-position to the iridium

(157) Synthesis of Ir(LH35-Br).sub.3:

(158) ##STR00714##

(159) 5.6 g (31.5 mmol) of N-bromosuccinimide are added in one portion to a suspension, stirred at 30° C., of 9.8 g (10 mmol) of Ir(LH35).sub.3 in 500 ml of DCM, and the mixture is then stirred for a further 20 h. After removal of about 450 ml of the DCM in vacuo, 100 ml of methanol are added to the yellow suspension, the solid is filtered off with suction, washed three times with about 30 ml of methanol and then dried in vacuo. Yield: 11.4 g (9.3 mmol), 953%; purity: >99.0% according to NMR.

(160) The following compounds can be prepared analogously:

(161) TABLE-US-00039 Ex. Complex Brominated complex Yield Ir(LH20-Br).sub.3 90% Ir(LH23-Br).sub.3 88% Ir(LH26-Br).sub.3 0 85% Ir(LH33-Br).sub.3 87% Ir(LH38-Br).sub.3 90% Ir500-Br.sub.2 85% Ir501-Br.sub.2 91% Ir505-Br.sub.2 0 90% Ir529-Br.sub.2 88% Ir534-Br 89% Ir535-Br 91% Ir541-Br 85% Ir563-Br 0 87%
2) Suzuki Coupling to the Brominated Fac-Iridium Complexes:
Variant a, Two-Phase Reaction Mixture:

(162) 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, 12-20 mmol of the boronic acid or boronic acid ester per Br function and 40-80 mmol of tripotassium phosphate in a mixture of 300 ml of toluene, 100 ml of dioxane and 300 ml of water, and the mixture is heated under reflux for 16 h. After cooling, 500 ml of water and 200 ml of toluene are added, the aqueous phase is separated off, the organic phase is washed three times with 200 ml of water, once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. The solid material is filtered off through a Celite bed and rinsed with toluene, the toluene is removed virtually completely in vacuo, 300 ml of methanol are added, the precipitated crude product is filtered off with suction, washed three times with 50 ml of methanol each time and dried in vacuo. The crude product is passed through a silica-gel column 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.

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

(164) 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, 12-20 mmol of the boronic acid or boronic acid ester per Br function and 60-100 mmol of the base (potassium fluoride, tripotassium phosphate (anhydrous or monohydrate or trihydrate), potassium carbonate, caesium carbonate, etc.) and 100 g of glass beads (diameter 3 mm) in 100 ml-500 ml of an aprotic solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.), and the mixture is heated under reflux for 1-24 h. Alternatively, other phosphines, such as tri-tert-butylphosphine, SPhos, XPhos, RuPhos, XanthPhos, etc., can be employed, where the preferred phosphine:palladium ratio in the case of these phosphines is 2:1 to 1.2:1. The solvent is removed in vacuo, the product is taken up in a suitable solvent (toluene, dichloromethane, ethyl acetate, etc.) and purified as described under Variant A.

(165) Synthesis of Ir600:

(166) ##STR00741##
Variant A:

(167) Use of 12.2 g (10.0 mmol) of Ir(LH35-Br).sub.3 and 4.9 g (40.0 mmol) of phenyl-boronic acid [98-80-6], 17.7 (60 mmol) of tripotassium phosphate (anhydrous), 183 mg (0.6 mmol) of tri-o-tolylphosphine [6163-58-2], 23 mg (0.1 mmol) of palladium(II) acetate, 300 ml of toluene, 100 ml of dioxane and 300 ml of water, 100° C., 12 h. Chromatographic separation on silica gel with toluene/ethyl acetate (90:10, w) twice. Yield: 6.3 g (5.2 mmol), 52%; purity: about 99.9% according to HPLC.

(168) The following compounds can be prepared analogously:

(169) TABLE-US-00040 Complex Boronic acid Ex. Variant Product Yield Ir601 Ir(LH38-Br).sub.3 1233200-59-3 A Chromatographic separation using toluene 57% Ir602 Ir(LH33-Br).sub.3 84110-40-7 B SPhos:Pd(ac).sub.2/2:1 K.sub.3PO.sub.4 * 3H.sub.2O Toluene Chromatographic separation using toluene 53% Ir603 Ir(LH26-Br).sub.3 5122-95-2 A Chromatographic separation using toluene 64% Ir604 Ir(LH20-Br).sub.3 84110-40-7 B SPhos:Pd(ac).sub.2/2:1 K.sub.3PO.sub.4 * 3H.sub.2O Toluene Chromatographic separation using toluene 61% Ir605 Ir500-Br.sub.2 100379-00-8 B SPhos:Pd(ac).sub.2/2:1 Cs.sub.2CO.sub.3/dioxane Chromatographic separation using tol/DCM (95:5 vv) 33% Ir606 Ir529-Br.sub.2 1251825-65-6 A Chromatographic separation using n-heptane/EA (90:10) 58% Ir607 Ir535-Br 654664-63-8 A Chromatographic separation using n-heptane/DCM (90:10) 51%
3) Buchwald Coupling to the Iridium Complexes:

(170) 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, 12-20 mmol of the diarylamine or carbazole p[er bromine function, 1.1 molar amount of sodium tert-butoxide per amine employed or 80 mmol of tripotassium phosphate (anhydrous) in the case of carbazoles, 100 g of glass beads (diameter 3 mm) and 300-500 ml of toluene or o-xylene in the case of carbazoles, and the mixture is heated under reflux for 16-30 h with vigorous stirring. After cooling, 500 ml of water are added, the aqueous phase is separated off, and the organic phase is washed twice with 200 ml of water and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. The solid material is filtered off through a Celite bed and rinsed with toluene or o-xylene, 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 50 ml of EtOH each time and dried in vacuo. The crude product is purified by chromatography on silica gel 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.

(171) Synthesis of Ir700:

(172) ##STR00749##

(173) Use of 12.2 g (10 mmol) of Ir(LH35-Br).sub.3 and 14.5 g (40 mmol) of N-[1,1′-biphenyl]-4-yl-9,9-dimethyl-9H-fluoren-2-amine [897671-69-1]. Heating. Yield: 8.5 g (4.1 mmol), 41%; purity: about 99.8% according to HPLC.

(174) The following compounds can be prepared analogously:

(175) TABLE-US-00041 Product Starting material Ex. Amine or carbazole Yield Ir701 0 40% Ir702 45% Ir703 47% Ir704 37%
4) Cyanation of the Iridium Complexes:

(176) A mixture of 10 mmol of the brominated complex, 13 mmol of copper(I) cyanide per bromine function and 300 ml of NMP is stirred at 200° C. for 20 h. After cooling, the solvent is removed in vacuo, the residue is taken up in 500 ml of dichloromethane, the copper salts are filtered off via Celite, the dichloromethane is evaporated virtually to dryness in vacuo, 100 ml of ethanol are added, the precipitated solid is filtered off with suction, washed twice with 50 ml of ethanol each time and dried in vacuo. Chromatography or hot extraction and fractional sublimation of the crude product as described in C: Synthesis of the metal complexes, 1) Homoleptic tris-facial iridium complexes of the phenylpyridine, phenylimidazole or phenylbenzimidazole type: variant A.

(177) Synthesis of Ir800:

(178) ##STR00754##

(179) Use of 12.2 g (10 mmol) of Ir(LH35-Br).sub.3 and 3.5 g (39 mmol) of copper(I) cyanide. Sublimation. Yield: 4.6 g (4.3 mmol), 43%; purity: about 99.8% according to HPLC.

(180) The Following Compounds can be Prepared Analogously:

(181) TABLE-US-00042 Product Ex. Starting material Yield Ir801 35% Ir802 37% Ir803 44%
5) Borylation of the Iridium Complexes:

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

(183) Synthesis of Ir900:

(184) ##STR00758##

(185) Use of 12.2 g (10 mmol) of Ir(LH35-Br).sub.3 and 9.1 g (36 mmol) of bis(pinacolato)diborane [73183-34-3], DMSO, 120° C., 6 h, taking-up and Celite filtration in THF, recrystallisation from THF:methanol. Yield: 6.8 g (5.0 mmol), 50%; purity: about 99.8% according to HPLC.

(186) The following compounds can be prepared analogously:

(187) TABLE-US-00043 Ex. Starting material Product Yield Ir901 0 60% Ir902 64%
6) Suzuki Coupling to the Borylated Fac-Iridium Complexes:
Variant A, Two-Phase Reaction Mixture:

(188) 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 borylated complex, 12-20 mmol of aryl bromide per (RO).sub.2B function and 80 mmol of tripotassium phosphate in a mixture of 300 ml of toluene, 100 ml of dioxane and 300 ml of water, 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, and the organic phase is washed three times with 200 ml of water, once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. The mixture is filtered through a Celite bed, the latter is rinsed with toluene, the toluene is removed virtually completely in vacuo, 300 ml of methanol are added, and the crude product which has precipitated out is filtered off with suction, washed three times with 50 ml of methanol each time and dried in vacuo. The crude product is passed through a silica-gel column 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., where the sublimation is preferably carried out in the form of a fractional sublimation.

(189) Variant B, Single-Phase Reaction Mixture:

(190) 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 borylated complex, 12-20 mmol of aryl bromide per (RO).sub.2B function and 60-100 mmol of the base (potassium fluoride, tripotassium phosphate (anhydrous, monohydrate or trihydrate), potassium carbonate, caesium carbonate, etc.) and 100 g of glass beads (diameter 3 mm) in 100 ml-500 ml of an aprotic solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.), and the mixture is heated under reflux for 1-24 h. Alternatively, other phosphines, such as tri-tert-butylphosphine, SPhos, XPhos, RuPhos, XanthPhos, etc., can be employed, where in the case of these phosphines the preferred phosphine:palladium ratio is 2:1 to 1.2:1. The solvent is removed in vacuo, and the product is taken up in a suitable solvent (toluene, dichloromethane, ethyl acetate, etc.) and purified as described under variant A.

(191) Synthesis of Ir600:

(192) ##STR00763##
Variant A:

(193) Use of 13.6 g (10.0 mmol) of Ir900 and 4.2 ml (40.0 mmol) of bromobenzene [108-86-1], 17.7 g (60 mmol) of tripotassium phosphate (anhydrous), 183 mg (0.6 mmol) of tri-o-tolylphosphine [6163-58-2], 23 mg (0.1 mmol) of palladium(II) acetate, 300 ml of toluene, 100 ml of dioxane and 300 ml of water, 100° C., 12 h. Chromatographic separation on silica gel using toluene/ethyl acetate (90:10, vv) twice. Yield: 6.3 g (5.2 mmol), 52%; purity: about 99.9% according to HPLC.

(194) The following compounds can be prepared analogously:

(195) TABLE-US-00044 Complex Boronic acid Ex. Variant Product Yield Ir608 Ir901 1153-85-1 A Chromatographic separation using toluene 63% Ir609 Ir902 1369587-63-2 A Chromatographic separation using toluene 55%
Polymers Containing the Metal Complexes:
General Polymerisation Procedure for the Bromides or Boronic Acid Derivatives as Polymerisable Group, Suzuki Polymerisation
Variant A—Two-Phase Reaction Mixture:

(196) The monomers (bromides and boronic acids or boronic acid esters, purity according to HPLC>99.8%) in the composition indicated in the table are dissolved or suspended in a mixture of 2 parts by volume of toluene:6 parts by volume of dioxane:1 part by volume of water in a total concentration of about 100 mmol/l. 2 mol equivalents of tripotassium phosphate per Br functionality employed are then added, the mixture is stirred for a further 5 min., 0.03 to 0.003 mol equivalent of tri-ortho-tolylphosphine and then 0.005 to 0.0005 mol equivalent of palladium(II) acetate (phosphine to Pd ratio preferably 6:1) per Br functionality employed are then added, and the mixture is heated under reflux for 2-3 h with very vigorous stirring. If the viscosity of the mixture increases excessively, it can be diluted with a mixture of 2 parts by volume of toluene:3 parts by volume of dioxane. After a total reaction time of 4-6 h, 0.05 mol equivalent per boronic acid functionality employed of a monobromoaromatic compound are added for end capping, and then, 30 min. later, 0.05 mol equivalent per Br functionality employed of a monoboronic acid or a monoboronic acid ester is added, and the mixture is boiled for a further 1 h. After cooling, the mixture is diluted with 300 ml of toluene. The aqueous phase is separated off, the organic phase is washed twice with 300 ml of water each time, dried over magnesium sulfate, filtered through a Celite bed in order to remove palladium and then evaporated to dryness. The crude polymer is dissolved in THF (concentration about 10-30 g/l), and the solution is allowed to run slowly, with very vigorous stirring, into twice the volume of methanol. The polymer is filtered off with suction and washed three times with methanol. The reprecipitation process is repeated five times, the polymer is then dried to constant weight at 30-50° C. in vacuo.

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

(198) 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 (anhydrous, monohydrate or trihydrate), 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, SPhos, XPhos, RuPhos, XanthPhos, 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.

(199) Monomers M/End Cappers E:

(200) TABLE-US-00045 M1 M2 M3 M4 0 E1 E2
Polymers:
Composition of the Polymers, Mol %:

(201) TABLE-US-00046 M1 M2 M3 M4 Polymer [%] [%] [%] [%] Ir complex/[%] P1 — 30 — 45 Ir(LH35—Br).sub.3/10 P2 — 30 — 40 Ir500—Br.sub.2/10 P3 20 30 25 20 Ir902/5
Molecular Weights and Yield of the Polymers According to the Invention:

(202) TABLE-US-00047 Polymer Mn [gmol.sup.−1] Polydispersity Yield P1 180,000 4.8 56% P2 250,000 2.3 61% P3 310,000 2.4 66%

(203) Comparison of the Solubility of the Complexes in Organic Solvents:

(204) The complexes according to the invention have the solubility shown in the table, in the solvents indicated at 25° C. Comparison with the complexes without the cyclic group according to the invention shows that the solubility of the complexes according to the invention is significantly greater (factor about 5-50).

(205) TABLE-US-00048 Comparative complex Complex Ex. Solvent Solubility Solubility [g/ml] Sol1 Toluene Sol2 o-Xylene Sol3 3-Phenoxy- toluene Sol4 Toluene Sol5 Toluene 0 Sol6 Toluene Sol7 Toluene Sol8 Toluene Sol9 Toluene Sol10 Toluene 0 Sol11 Cyclohexane Sol12 Toluene Sol13 Toluene Sol14 Toluene Sol15 Toluene 00 01 Sol16 Toluene 02 03 Sol17 Toluene 04 05
Sublimation of the Complexes:

(206) The complexes according to the invention have the sublimation temperature and rate shown in the table at a base pressure of about 10.sup.−5 mbar. Comparison with complexes without the bicyclic group according to the invention shows that the sublimation temperature of the complexes according to the invention is lower and the sublimation rate is significantly greater. In addition, the complexes according to the invention are stable under the sublimation conditions.

(207) TABLE-US-00049 Ex. Comparative complex Complex Sub1 06 07 Sub2 08 09 Sub3 0 Sub4 Sub5 Sub6 Sub7 Sub8 0 Sub9

Example: Production of OLEDs

(208) 1) Vacuum-Processed Devices:

(209) 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).

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

(211) 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 co-evaporation. An expression such as M3:M2:Ir(LH1).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(LH1).sub.3 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials. The precise structure of the OLEDs is shown in Table 1. The materials used for the production of the OLEDs are shown in Table 7.

(212) 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.

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

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

(215) TABLE-US-00050 TABLE 1 Structure of the OLEDs HTL2 EBL EML HBL ETL Ex. Thickness Thickness Thickness Thickness Thickness Orange - red OLEDs D-IrR1 HTM — M7:M8:Ir-R1 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-IrR2 HTM — M7:M8:Ir-R2 — ETM1:ETM2 270 nm (60%:30%:10%) (50%:50%) 35 nm 35 nm D-IrR3 HTM — M7:M8:Ir-R3 — ETM1:ETM2 270 nm (60%:30%:10%) (50%:50%) 35 nm 35 nm D-Ir(LH4).sub.3 HTM — M7:M8:Ir(LH4).sub.3 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir(LH9).sub.3 HTM — M7:M8:Ir(LH9).sub.3 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir(LH10).sub.3 HTM — M7:M8:Ir(LH10).sub.3 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir(LH26).sub.3 HTM — M7:M8:Ir(LH26).sub.3 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir(LH27).sub.3 HTM — M7:M8:Ir(LH27).sub.3 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir(LH32).sub.3 HTM — M7:M8:Ir(LH32).sub.3 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir(LH33).sub.3 HTM — M7:M8:Ir(LH33).sub.3 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir(LH61).sub.3 HTM — M7:M8:Ir(LH61).sub.3 — ETM1:ETM2 270 nm (60%:30%:10%) (50%:50%) 35 nm 35 nm D-Ir503 HTM — M7:M8:Ir503 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir509 HTM — M7:M8:Ir509 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir516 HTM — M7:M8:Ir516 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir517 HTM — M7:M8:Ir517 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir520 HTM — M7:M8:Ir520 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir521 HTM — M7:M8:Ir521 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir522 HTM — M7:M8:Ir522 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir523 HTM — M7:M8:Ir523 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir524 HTM — M7:M8:Ir524 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir539 HTM — M7:M8:Ir539 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir547 HTM — M7:M8:Ir547 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir548 HTM — M7:M8:Ir548 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm D-Ir554 HTM — M7:M8:Ir554 — ETM1:ETM2 270 nm (65%:30%:5%) (50%:50%) 35 nm 35 nm Yellow OLEDs D-Ir-Y1 HTM — M7:M8:Ir-Y1 — ETM1:ETM2 240 nm (58%:30%:12%) (50%:50%) 25 nm 40 nm D-Ir-Y2 HTM — M7:M8:Ir-Y2 — ETM1:ETM2 240 nm (62%:30%:8%) (50%:50%) 25 nm 40 nm D-Ir(LH6).sub.3 HTM — M7:M8:Ir(LH6).sub.3 — ETM1:ETM2 240 nm (62%:30%:8%) (50%:50%) 25 nm 40 nm D-Ir(LH8).sub.3 HTM — M7:M8:Ir(LH8).sub.3 — ETM1:ETM2 240 nm (60%:30%:10%) (50%:50%) 25 nm 40 nm D-Ir505 HTM — M7:M8:Ir505 — ETM1:ETM2 240 nm (62%:30%:8%) (50%:50%) 25 nm 40 nm D-Ir508 HTM — M7:M8:Ir508 — ETM1:ETM2 240 nm (62%:30%:8%) (50%: 50%) 25 nm 40 nm D-Ir512 HTM — M7:M8:Ir512 — ETM1:ETM2 240 nm (62%:30%:8%) (50%:50%) 25 nm 40 nm D-Ir537 HTM — M7:M8:Ir537 — ETM1:ETM2 240 nm (62%:30%:8%) (50%:50%) 25 nm 40 nm Green OLEDs D-Ir-G1 HTM — M7:M8:Ir-G1 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir-G2 HTM — M7:M8:Ir-G2 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir-G4 HTM — M7:M8:Ir-G4 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir-G4b NPB — CBP:Ir-G4 BCP AlQ (20 nm) 40 nm (80%:20%) 10 nm LiQ (2 nm) 30 nm D-Ir(LH1).sub.3 HTM — M7:M8:Ir(LH1).sub.3 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir(LH1).sub.3 HTM — M7:M8:Ir(LH1).sub.3 HBM2 ETM1:ETM2 220 nm (55%:30%:15%) 10 nm (50%:50%) 25 nm 30 nm D-Ir(LH3).sub.3 HTM — M7:M8:Ir(LH3).sub.3 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir(LH7).sub.3 HTM — M7:M8:Ir(LH7).sub.3 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir(LH16).sub.3 HTM — M7:M8:Ir(LH16).sub.3 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir(LH35).sub.3 HTM — M7:M8:Ir(LH35).sub.3 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir(LH36).sub.3 HTM — M7:M8:Ir(LH36).sub.3 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir(LH41).sub.3 HTM — M7:M8:Ir(LH41).sub.3 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir(LH42).sub.3 HTM — M7:M8:Ir(LH42).sub.3 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir(LH49).sub.3 HTM — M7:M8:Ir(LH49).sub.3 HBM2 ETM1:ETM2 220 nm (62%:30%:8%) 10 nm (50%:50%) 30 nm 30 nm D-Ir(LH57).sub.3 HTM — M7:M8:Ir(LH57).sub.3 HBM2 ETM1:ETM2 220 nm (62%:30%:8%) 10 nm (50%:50%) 30 nm 30 nm D-Ir(LH58).sub.3 HTM — M7:M8:Ir(LH58).sub.3 HBM2 ETM1:ETM2 220 nm (62%:30%:8%) 10 nm (50%:50%) 30 nm 30 nm D-Ir(LH59).sub.3 HTM — M7:M8:Ir(LH59).sub.3 HBM2 ETM1:ETM2 220 nm (62%:30%:8%) 10 nm (50%:50%) 30 nm 30 nm D-Ir(LH60).sub.3 HTM — M7:M8:Ir(LH60).sub.3 HBM2 ETM1:ETM2 220 nm (62%:30%:8%) 10 nm (50%:50%) 30 nm 30 nm D-Ir500 HTM — M7:M8:Ir500 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir501 HTM — M7:M8:Ir501 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir502 HTM — M7:M8:Ir502 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir506 HTM — M7:M8:Ir506 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir507 HTM — M7:M8:Ir507 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir510 HTM — M7:M8:Ir510 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir511 HTM — M7:M8:Ir511 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir519 HTM — M7:M8:Ir519 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir526 HTM — M7:M8:Ir526 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir527 HTM — M7:M8:Ir527 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir529 HTM — M7:M8:Ir529 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir530 HTM — M7:M8:Ir530 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir531 HTM — M7:M8:Ir531 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir532 HTM — M7:M8:Ir532 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir533 HTM — M7:M8:Ir533 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir534 HTM — M7:M8:Ir534 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir536 HTM — M7:M8:Ir536 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir538 HTM — M7:M8:Ir538 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir543 HTM — M7:M8:Ir543 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir556 HTM — M7:M8:Ir556 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir557 HTM — M7:M8:Ir557 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir562 HTM — M7:M8:Ir562 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir563 HTM — M7:M8:Ir563 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir570 HTM — M7:M8:Ir570 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir571 HTM — M7:M8:Ir571 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Ir572 HTM — M7:M8:Ir572 HBM2 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm D-Pt(LH43) HTM — M7:M8:Pt(LH43) HBM2 ETM1:ETM2 220 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D-Pt(LH45) HTM — M7:M8:Pt(LH45) HBM2 ETM1:ETM2 220 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm Blue OLEDs D-Ir-B1 HTM EBM M1:M4:Ir-B1 HBM1 ETM1:ETM2 180 nm 10 nm (60%:35%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir-B2 HTM EBM M10:M4:Ir-B2 HBM1 ETM1:ETM2 180 nm 10 nm (45%:45%:10%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(LH23).sub.3 HTM EBM M10:M4:fac-Ir(LH23).sub.3 HBM1 ETM1:ETM2 180 nm 10 nm (45%:45%:10%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(LH25).sub.3 HTM EBM M10:M4:fac-Ir(LH25).sub.3 HBM1 ETM1:ETM2 180 nm 10 nm (45%:45%:10%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(LH40).sub.3 HTM EBM M1:M4:Ir(LH40).sub.3 HBM1 ETM1:ETM2 180 nm 10 nm (60%:35%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir561 HTM EBM M1:M4:Ir561 HBM1 ETM1:ETM2 180 nm 10 nm (60%:35%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Pt(LH44) HTM EBM M10:M4:Pt(LH44) HBM1 ETM1:ETM2 180 nm 10 nm (45%:45%:10%) 10 nm (50%:50%) 25 nm 20 nm D-Pt(LH46) HTM EBM M10:M4:Pt(LH46) HBM1 ETM1:ETM2 180 nm 10 nm (45%:45%:10%) 10 nm (50%:50%) 25 nm 20 nm D-Pt(LH47) HTM EBM M10:M4 Pt(LH47) HBM1 ETM1:ETM2 180 nm 10 nm (45%:45%:10%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(LH51) HTM EBM M10:M4:Ir(LH51) HBM1 ETM1:ETM2 180 nm 10 nm (45%:45%:10%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(LH52) HTM EBM M10:M4:Ir(LH52) HBM1 ETM1:ETM2 180 nm 10 nm (45%:45%:10%) 10 nm (50%:50%) 25 nm 20 nm

(216) TABLE-US-00051 TABLE 2 Results of the vacuum-processed OLEDs EQE (%) Voltage (V) CIE x/y Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Orange - red OLEDs LT80 (h) 1000 cd/m.sup.2 D-IrR1 13.2 2.9 0.67/0.33 13000 D-IrR2 19.1 3.2 0.66/0.35 23000 D-IrR3 15.1 3.3 0.68/0.31  8000 D-Ir(LH4).sub.3 18.5 3.1 0.69/0.30 — D-Ir(LH9).sub.3 19.6 3.0 0.65/0.34 17000 D-Ir(LH10).sub.3 18.9 3.1 0.69/0.30 — D-Ir(LH26).sub.3 18.5 3.0 0.69/0.30 19000 D-Ir(LH27).sub.3 18.4 3.0 0.69/0.30 18000 D-Ir(LH32).sub.3 18.9 3.2 0.70/0.30 18000 D-Ir(LH33).sub.3 19.2 3.1 0.64/0.35 14000 D-Ir(LH61).sub.3 18.0 3.0 0.70/0.30 21000 D-Ir503 19.3 3.0 0.64/0.35 22000 D-Ir509 19.5 3.1 0.64/0.35 23000 D-Ir516 17.1 3.1 0.63/0.36 — D-Ir517 17.4 3.2 0.65/0.34 11000 D-Ir520 17.2 3.1 0.63/0.36 18000 D-Ir521 17.8 3.1 0.63/0.36 18000 D-Ir522 18.2 3.1 0.63/0.36 20000 D-Ir523 18.0 3.0 0.66/0.33 22000 D-Ir524 19.3 3.0 0.65/0.34 21000 D-Ir539 19.5 3.1 0.66/0.34 — D-Ir547 18.9 3.0 0.67/0.31 20000 D-Ir548 19.5 3.0 0.68/0.32 22000 D-Ir554  19.688 3.0 0.64/0.35 19000 Yellow OLEDs D-Ir-Y1 19.6 2.8 0.39/0.62 35000 D-Ir-Y2 22.1 2.9 0.44/0.56 34000 D-Ir(LH6).sub.3 23.7 3.0 0.47/0.52 38000 D-Ir(LH8).sub.3 21.3 3.0 0.45/0.55 — D-Ir505 23.9 2.9 0.44/0.55 41000 D-Ir508 22.6 3.0 0.59/0.38 — D-Ir537 22.1 2.9 0.46/0.52 40000 Green OLEDs D-Ir-G1 18.1 3.3 0.32/0.64  7000 D-Ir-G2 19.2 3.2 0.35/0.62 16000 D-Ir-G4 16.3 3.7 0.34/0.63  600 D-Ir-G4b 14.6 5.8 0.34/0.63  160 D-Ir(LH1).sub.3 23.3 3.2 0.33/0.64 18000 D-Ir(LH1).sub.3 22.9 3.3 0.36/0.61 16000 D-Ir(LH3).sub.3 24.1 3.3 0.35/0.62 20000 D-Ir(LH7).sub.3 23.7 3.3 0.34/0.64 21000 D-Ir(LH16).sub.3 24.3 3.3 0.35/0.63 24000 D-Ir(LH35).sub.3 22.8 3.2 0.33/0.64 22000 D-Ir(LH36).sub.3 23.4 3.2 0.33/0.65 25000 D-Ir(LH41).sub.3 24.5 3.3 0.35/0.62 25000 D-Ir(LH42).sub.3 24.3 3.3 0.35/0.61 24000 D-Ir(LH49).sub.3 20.7 3.4 0.41/0.56 — D-Ir(LH57).sub.3 22.3 3.3 0.34/0.64 21000 D-Ir(LH58).sub.3 23.0 3.2 0.32/0.65 23000 D-Ir(LH59).sub.3 22.9 3.3 0.34/0.63 — D-Ir(LH60).sub.3 21.4 3.3 0.39/0.58 — D-Ir500 23.3 3.2 0.33/0.63 22000 D-lr501 24.0 3.1 0.35/0.62 27000 D-Ir502 23.9 3.2 0.33/0.63 20000 D-Ir506 24.0 3.1 0.33/0.63 20000 D-Ir507 22.8 3.2 0.38/0.59 20000 D-Ir510 23.3 3.3 0.39/0.58 18000 D-Ir511 24.1 3.2 0.34/0.63 23000 D-Ir519 23.1 3.4 0.18/0.53 — D-Ir526 24.4 3.2 0.34/0.63 23000 D-Ir527 24.5 3.2 0.34/0.62 24000 D-Ir529 24.3 3.2 0.33/0.63 25000 D-Ir530 24.2 3.2 0.33/0.63 24000 D-Ir531 24.4 3.2 0.33/0.63 25000 D-Ir532 24.6 3.2 0.33/0.63 23000 D-Ir533 24.5 3.1 0.35/0.62 26000 D-Ir534 24.1 3.2 0.33/0.63 — D-Ir536 24.4 3.2 0.33/0.62 25000 D-Ir538 24.0 3.2 0.35/0.61 24000 D-Ir543 24.3 3.3 0.33/0.63 25000 D-Ir556 22.8 3.2 0.33/0.62 22000 D-Ir557 23.9 3.2 0.33/0.62 22000 D-Ir562 24.0 3.3 0.33/0.63 25000 D-Ir563 24.3 3.3 0.33/0.63 — D-Ir570 23.9 3.2 0.33/0.62 20000 D-Ir571 24.1 3.2 0.34/0.62 22000 D-Ir572 20.4 3.3 0.26/0.51 — D-Pt(LH43) 19.9 3.2 0.35/0.61 16000 D-Pt(LH45) 20.9 3.2 0.35/0.61 18000 Blue OLEDs LT50 (h) 1000 cd/m.sup.2 D-Ir-B1 16.1 4.9 0.18/0.37  1100 D-Ir-B2  3.0 5.2 0.16/0.07   60 D-Ir(LH23).sub.3  9.4 5.4 0.15/0.17  100 D-Ir(LH25).sub.3  6.5 5.9 0.15/0.11 — D-Ir(LH40).sub.3 21.9 4.1 0.15/0.26  500 D-Ir561 21.0 4.3 0.16/0.29  700 D-Pt(LH44) 19.5 3.5 0.18/0.38 16000 D-Pt(LH46) 12.5 5.3 0.16/0.25 — D-Pt(LH47) 12.1 5.1 0.16/0.26 — D-Ir(LH51) 13.9 5.1 0.15/0.23 — D-Ir(LH52) 14.4 5.0 0.15/0.22 —
2) Solution-Processed Devices:
A: From Soluble Functional Materials

(217) 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). 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 of type 1 comprise an emission layer comprising (polystyrene):M5:M6:Ir(LH).sub.3 (20%:35%:35%:10%) and those of type 2 comprise an emission layer comprising (polystyrene):M5:M6:Ir(LH6).sub.3:Ir(LH).sub.3 (20%:25%:40%:10%:5%). 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 4 summarises the data obtained.

(218) TABLE-US-00052 TABLE 3 Results with solution-processed materials Emitter EQE (%) Voltage (V) LT50 (h) Ex. Device 1000 cd/m.sup.2 1000 cd/m.sup.2 CIE x/y 1000 cd/m.sup.2 Orange and red OLEDs Sol-D-Ir-R2 Ir-R2 18.8 3.6 0.67/0.33  20000 Type 2 Sol-D-Ir(LH28).sub.3 Ir(LH28).sub.3 18.8 3.9 0.65/0.35 150000 Type 1 Sol-D-Ir(LH29).sub.3 Ir(LH29).sub.3 19.5 3.7 0.61/0.38 — Type 1 Sol-D-Ir(LH30).sub.3 Ir(LH30).sub.3 19.1 3.7 0.69/0.30 180000 Type 2 Sol-D-Ir(LH31).sub.3 Ir(LH31).sub.3 19.5 3.6 0.68/0.31 — Type 1 Sol-D-Ir(LH34).sub.3 Ir(LH34).sub.3 19.9 3.7 0.65/0.35 — Type 1 Sol-D-Ir518 Ir518 17.1 3.7 0.70/0.30 — Type 1 Sol-D-Ir523 Ir523 19.1 3.8 0.64/0.35 160000 Type 2 Sol-D-Ir525 Ir525 19.8 3.8 0.63/0.36 — Type 2 Sol-D-Ir549 Ir549 19.5 3.8 0.65/0.35 — Type 2 Sol-D-Ir550 Ir550 19.0 3.9 0.62/0.35 170000 Type 2 Sol-D-Ir551 Ir551 20.0 3.8 0.67/0.33 200000 Type 2 Sol-D-Ir552 Ir552 19.7 3.9 0.68/0.32 — Type 2 Sol-D-Ir553 Ir553 20.0 3.9 0.68/0.32 — Type 2 Sol-D-Ir555 Ir555 20.5 3.8 0.65/0.34 — Type 2 Sol-D-Ir569 Ir569 20.2 3.8 0.65/0.33 — Type 2 Sol-D-Ir602 Ir602 19.0 4.0 0.63/0.36 — Type 2 Sol-D-Ir603 Ir603 18.1 3.9 0.66/0.33 — Type 2 Sol-D-Ir700 Ir700 17.0 3.7 0.62/0.37 — Type 2 Yellow OLEDs of type 1 Sol-D-Ir-Y3 Ir-Y3 19.7 3.9 0.48/0.49 120000 Sol-D-Ir(LH6).sub.3 Ir(LH6).sub.3 21.5 4.1 0.45/0.54 200000 Sol-D-Ir(LH11).sub.3 Ir(L11).sub.3 22.1 4.3 0.53/0.46 — Sol-D-Ir(LH53).sub.3 Ir(L53).sub.3 21.0 4.3 0.44/0.54 140000 Sol-D-Ir(LH55).sub.3 Ir(L55).sub.3 21.2 4.4 0.43/0.55 — Sol-D-Ir513 Ir513 22.4 4.2 0.44/0.55 250000 Sol-D-Ir541 Ir541 22.1 4.1 0.45/0.54 — Sol-D-Ir558 Ir558 21.4 4.1 0.46/0.53 — Sol-D-Ir560 Ir560 21.7 4.1 0.47/0.48 — Sol-D-Ir566 Ir566 21.9 4.1 0.46/0.53 — Sol-D-Ir608 Ir608 19.1 3.9 0.38/0.57 — Sol-D-Ir609 Ir609 20.9 4.2 0.42/0.54 — Sol-D-Ir701 Ir701 19.8 4.0 0.41/0.56 220000 Green - cyan OLEDs of type 1 Sol-D-Ir-G3 Ir-G3 18.8 4.4 0.33/0.63 100000 Sol-D-Ir-G5 Ir-G5 18.3 4.6 0.34/0.62  3000 Sol-D-Ir-G6 Ir-G6 21.3 4.7 0.33/0.63  27000 Sol-D-Ir-G7 Ir-G7 21.6 4.7 0.33/0.63  60000 Sol-D-Ir(LH1).sub.3 Ir(LH1).sub.3 22.2 4.6 0.33/0.65 190000 Sol-D-Ir(LH5).sub.3 Ir(LH5).sub.3 22.7 4.7 0.33/0.64 220000 Sol-D-Ir(LH12).sub.3 Ir(LH12).sub.3 21.9 4.6 0.34/0.62 — Sol-D-Ir(LH13).sub.3 Ir(LH13).sub.3 21.8 4.6 0.44/0.52 220000 Sol-D-Ir(LH15).sub.3 Ir(LH15).sub.3 22.1 4.6 0.34/0.61 200000 Sol-D-Ir(LH20).sub.3 Ir(LH20).sub.3 19.3 4.6 0.22/0.42 — Sol-D-Ir(LH21).sub.3 Ir(LH21).sub.3 19.1 4.7 0.21/0.43 — Sol-D-Ir(LH37).sub.3 Ir(LH37).sub.3 21.1 4.6 0.36/0.61 190000 Sol-D-Ir(LH38).sub.3 Ir(LH38).sub.3 21.6 4.6 0.35/0.63 — Sol-D-Ir(LH39).sub.3 Ir(LH39).sub.3 21.3 4.6 0.37/0.61 — Sol-D-Ir(LH54).sub.3 Ir(LH54).sub.3 21.6 4.6 0.34/0.63 200000 Sol-D-Ir(LH56).sub.3 Ir(LH56).sub.3 21.7 4.7 0.35/0.62 210000 Sol-D-Ir514 Ir514 22.3 4.5 0.34/0.63 210000 Sol-D-Ir515 Ir515 22.1 4.6 0.34/0.63 — Sol-D-Ir528 Ir528 21.5 4.7 0.35/0.62 — Sol-D-Ir535 Ir535 21.8 4.7 0.36/0.61 — Sol-D-Ir540 Ir540 22.2 4.6 0.34/0.63 — Sol-D-Ir542 Ir542 22.5 4.6 0.34/0.63 — Sol-D-Ir545 Ir545 21.4 4.6 0.28/0.49 — Sol-D-Ir546 Ir546 20.5 4.5 0.23/0.46 — Sol-D-Ir564 Ir564 21.8 4.6 0.33/0.64 — Sol-D-Ir565 Ir565 21.3 4.5 0.45/0.52 — Sol-D-Ir567 Ir567 22.3 4.7 0.33/0.63 180000 Sol-D-Ir568 Ir568 21.5 4.6 0.45/0.52 — Sol-D-Ir600 Ir600 20.2 4.5 0.34/0.64 — Sol-D-Ir601 Ir601 20.0 4.6 0.35/0.63 — Sol-D-Ir604 Ir604 19.8 4.6 0.23/0.46 — Sol-D-Ir605 Ir605 21.8 4.6 0.33/0.63 — Sol-D-Ir606 Ir606 20.9 4.5 0.23/0.46 — Sol-D-Ir607 Ir607 19.9 4.5 0.35/0.62 — Sol-D-Ir702 Ir702 20.8 4.6 0.45/0.52 — Sol-D-Ir703 Ir703 20.3 4.6 0.33/0.63 — Sol-D-Ir704 Ir704 19.7 4.4 0.32/0.62 — Sol-D-Ir800 Ir800 16.1 4.3 0.16/0.35 — Sol-D-Ir801 Ir801 16.7 4.5 0.17/0.40 — Sol-D-Ir803 Ir803 19.2 4.5 0.17/0.38 —
B: From Polymeric Functional Materials:

(219) Production of the OLEDs as described under A: For the production of the emission layer, the polymers according to the invention are dissolved in toluene. The typical solids content of such solutions is between 10 and 15 g/l if, as here, the typical layer thickness of 80 nm for a device is to be achieved by means of spin coating. The said OLED examples have not yet been optimised, Table 5 summarises the data obtained.

(220) TABLE-US-00053 TABLE 4 Results with solution-processed materials EQE (%) Voltage (V) CIE x/y Ex. Polymer 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Yellow OLEDs D-P3 P3 20.1 3.7 0.42/0.57 Green OLEDs D-P1 P1 20.5 4.0 0.33/0.61 D-P2 P2 20.6 4.1 0.32/0.63
3) White-Emitting OLED9

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

(222) TABLE-US-00054 TABLE 5 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:Ir521 M1:M4:Ir(LH40).sub.3 M3:Ir(LH1).sub.3 M3 ETM1:ETM2 230 nm (97%:3%) (65%:30%:5%) (95%:5%) 10 nm (50%:50%) 10 nm 8 nm 7 nm 30 nm

(223) TABLE-US-00055 TABLE 6 Device results EQE (%) Voltage (V) CIE x/y LT50 (h) Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 D-W1 20.9 5.7 0.42/0.38 5000

(224) TABLE-US-00056 TABLE 7 Structural formulae of the materials used 0 0 0