# US 7,745,627 B2 · Method for the production of heteroleptic ortho-metallated organometallic compounds

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- Number: US 7,745,627 B2
- Document ID: US7745627B2
- Status: Granted
- Kind: B2
- Application number: 10/577,617
- Filed: 2004-10-21
- Published: 2007-06-14
- Granted: 2010-06-29
- Earliest claimed: 2003-10-30
- Assignees: Merck Patent GmbH
- Inventors: Philipp Stössel; Arne Büsing; Ingrid Bach
- Web page: https://patentgrep.com/patent/US7745627B2

## CPC

- C07F 15/006: {Palladium compounds}
- C07F 15/0033: {Iridium compounds}
- C07F 15/0073: {Rhodium compounds}
- C07F 15/0086: {Platinum compounds}
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

The invention relates to a method for the production of high-purity, heteroleptic, orth-etallated, organometallic compounds of application as a functional material for colouring components in a wide range of applications within the widest sense of the electronics industry. A method is thus used for the cleavage of a bridged metal dimer with organometallic substances. Dihalo complexes, which may be used as monomers for polymerisations, in particular, may be produced thus.

## Claims

### Claim 1

A process for the preparation of compounds (I)
wherein
M is, identically or differently on each occurrence, Rh, Ir, Pd or Pt;
Z is, identically or differently on each occurrence, N or P;
A, A′ is, identically or differently on each occurrence, N, C—H or C—R or C—R′; or alternatively two adjacent ring atoms A-A or A′-A′ on each occurrence, identically or differently, stand for S, O, Se or N—R1, with the proviso that these units do not occur more than once per ring;
R, R′ is, identically or differently on each occurrence, F, Cl, Br, NO2, CN, a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, where one or more non-adjacent CH2 groups may be replaced by —CR1═CR1—, —C≡C—, —O—, —S—, —NR1—, or —CONR1— and where one or more H atoms may be replaced by F, or an aryl, heteroaryl, aryloxy or arylamino group having 4 to 14 C atoms, which may be substituted by one or more non-aromatic radicals R; where a plurality of substituents R on the same ring together may in turn define a further mono- or polycyclic, aliphatic or aromatic ring system;
R1 is, identically or differently on each occurrence, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms;
n is 1 for M=Pd or Pt and is 2 for M=Rh or Ir;
which comprises reacting a compound (Ia)
wherein
Y is on each occurrence, identically or differently, F, Cl, Br, I, OR1, R1COO, SR1, N(R1)2;
and the other symbols and indices are as defined for compound (I),
with an organometallic compound (Ib)
where Q stands for an alkali metal, an alkaline-earth metal or alkaline-earth metal halide, trialkyltin or zinc or a zinc halide, which may optionally also be substituted by further organic groups, and the other symbols and indices have the meaning given for compound (I).

### Claim 2 (depends on 1)

The process according to claim 1, wherein metal-containing starting materials are binuclear metal complexes of the formula (Ia), in which Y on each occurrence, identically or differently, denotes F, Cl, Br or OR1.

### Claim 3 (depends on 1)

The process according to claim 1, wherein Q represents an alkali metal or an alkaline-earth metal or alkaline-earth metal halide.

### Claim 4 (depends on 3)

The process according to claim 3, wherein Q stands for lithium, sodium or magnesium or a magnesium halide.

### Claim 5 (depends on 4)

The process according to claim 4, wherein Q stands for magnesium or a magnesium halide.

### Claim 6 (depends on 1)

The process according to claim 1, wherein the molar ratio of compound (Ia) to compound (Ib), is 1:2 to 1:50.

### Claim 7 (depends on 1)

The process according to claim 1, wherein said reaction of compound (Ia) with compound (Ib) is performed in a solvent selected from the group consisting of open-chain or cyclic ethers, open-chain or cyclic dialkylureas or HMPTA.

### Claim 8 (depends on 1)

The process according to claim 1, wherein the reaction is carried out in a temperature range from −78° C. to 150° C.

### Claim 9 (depends on 1)

The process according to claim 1, wherein the reaction is carried out over the course of 0.5 to 48 h.

### Claim 10 (depends on 1)

Process for the synthesis of dihalogenated tris-ortho-metallated rhodium and iridium complexes or monohalogenated bis-ortho-metallated palladium and platinum complexes, wherein a process according to claim 1 is used in one reaction step.

### Claim 11 (depends on 10)

The process according to claim 10, wherein it is carried out in accordance with scheme 2
or scheme 3
wherein
M is, identically or differently on each occurrence, Rh, Ir, Pd or Pt;
Z is, identically or differently on each occurrence, N or P;
A, A′ is, identically or differently on each occurrence, N, C—H or C—R or C—R′; or alternatively two adjacent ring atoms A-A or A′-A′ on each occurrence, identically or differently, stand for S, O, Se or N—R1, with the proviso that these units do not occur more than once per ring;
R, R′ is, identically or differently on each occurrence, F, Cl, Br, NO2, CN, a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, where one or more non-adjacent CH2 groups may be replaced by —CR1═CR1—, —C≡C—, —O—, —S—, —NR1—, or —CONR1— and where one or more H atoms may be replaced by F, or an aryl, heteroaryl, aryloxy or arylamino group having 4 to 14 C atoms, which may be substituted by one or more non-aromatic radicals R; where a plurality of substituents R on the same ring together may in turn define a further mono- or polycyclic, aliphatic or aromatic ring system;
R1 is, identically or differently on each occurrence, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms;
Y is on each occurrence, identically or differently, F, Cl, Br, I, OR1, R1COO, SR1, N(R1)2;
n is 1 for M=Pd or Pt and is 2 for M=Rh or Ir;
Q stands for an alkali metal, an alkaline-earth metal or alkaline-earth metal halide, trialkyltin or zinc or a zinc halide, which may optionally also be substituted by further organic groups
Hal is on each occurrence, identically or differently, Cl, Br, I; and
X is on each occurrence, identically or differently, N—R1, O, S or Se.