# US 7,153,806 B2 · Encapsulated oxo-bridged organometallic cluster catalyst and a process for the preparation thereof

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- Number: US 7,153,806 B2
- Document ID: US7153806B2
- Status: Granted
- Kind: B2
- Application number: 10/924,340
- Filed: 2004-08-23
- Published: 2005-08-18
- Granted: 2006-12-26
- Earliest claimed: 2001-06-28
- Assignees: Council of Scientific and Industrial Research
- Inventors: Darbha Srinivas; Suhas Arunkumar Chavan; Paul Ratnasamy
- Web page: https://patentgrep.com/patent/US7153806B2

## CPC

- B01J 31/1616: {Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts (catalysts comprising molecular sieves B01J29/00)}
- B01J 29/146: {Y-type faujasite}
- B01J 31/1805: {the ligands containing nitrogen}
- B01J 31/181: {Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine}
- B01J 31/2208: {Oxygen, e.g. acetylacetonates}
- B01J 31/2226: {Anionic ligands, i.e. the overall ligand carries at least one formal negative charge}
- C07C 51/265: having alkyl side chains which are oxidised to carboxyl groups
- B01J 31/04: containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)}
- B01J 31/28: of the platinum group metals, iron group metals or copper
- B01J 31/32: of manganese, technetium or rhenium
- B01J 2229/186: not in framework positions
- B01J 2229/34: Reaction with organic or organometallic compounds
- B01J 2231/70: Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J 2531/0222: Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
- B01J 2531/72: Manganese
- B01J 2531/845: Cobalt
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The present invention relates to a novel encapsulated organometallic cluster complex catalyst and to a process for the preparation thereof. The oxo-bridged organometallic cluster complex of the invention has at least one atom of cobalt and manganese encapsulated in micro and mesoporous porous solids like aluminosilicate zeolites, aluminophosphates, carbon molecular sieves, silica and is particularly effective for oxidation of aromatic alkyl groups to the carboxyl groups in high yields.

## Claims

### Claim 1

An encapsulated organometallic cluster complex catalyst wherein the organometallic cluster is of formula [MM′2(μ3-O)(RCOO)mLm′]L′n, wherein M and M′ are 3d or mid to late transition metal ions, R is selected from the group consisting of alkyl containing 1 to 5 carbon atoms, aryl, substituted alkyl and substituted aryl group; m is in the range of from 3 to 6, L is selected from the group consisting of RCOO, pyridine, nitrogen-containing organic bases, H2O, and organic solvents; L′ is a halide ion or halide containing ion and m′ and n are in the range of 0 to 3, said complex being encapsulated in a porous material.

### Claim 2 (depends on 1)

The encapsulated organometallic cluster complex catalyst as claimed in claim 1 wherein M and M′ are selected from the group consisting of Co or Mn.

### Claim 3 (depends on 1)

The encapsulated organometallic cluster complex catalyst as claimed in claim 1 wherein the catalyst is selected from the group consisting of CoMn2(μ3-O)(CH3COO)6, Co2Mn(μ3-O)(CH3COO)6, CoMn2(μ3-O)(CH3COO)6(pyridine)3, and Co2Mn(μ3-O)(CH3COO)6(pyridine)3.

### Claim 4 (depends on 1)

The encapsulated organometallic cluster complex catalyst as claimed in claim 1 wherein the porous material comprises micro and mesoporous materials selected from group consisting of aluminosilicate zeolites, aluminophosphates, silica and carbon molecular sieves.

### Claim 5

A process for the preparation of the encapsulated organometallic cluster complex of formula, [MM′2(μ3-O)(RCOO)mLm′]L′n, wherein M and M′ are 3d or mid to late transition metal ions R is selected from the group consisting of alkyl containing 1 to 5 carbon atoms, aryl substituted alkyl or substituted aryl group, m is in range of from 3 to 6, L is selected from the group consisting of RCOO, pyridine, nitrogen containing organic bases, H2O, and organic solvents, L′ is a halide ion or halide containing ion and m′ and n are each in the range of 0 to 3, said process comprising interacting an encapsulant with a mixture of solutions of sources of transition metal ions at a temperature in the range of 298° K to 358° K under constant stirring to obtain a solid product, washing and drying the solid product thoroughly at 390 to 410° K, and then adding to it an organic carboxylic acid, pyridine, salt of alkali metal and water, under constant agitation and pumping oxygen or air into the mixture for 2 to 4 h at 298° K and separating and drying the encapsulated complex at 298° K under vacuum to obtain the encapsulated oxo-bridged organometallic cluster catalyst.

### Claim 6 (depends on 5)

The process as claimed in claim 5 wherein the transition metal ions used are selected from cobalt and manganese ions.

### Claim 7 (depends on 6)

The process as claimed in claim 6 wherein the manganese ion source used is selected from the group consisting of manganese acetate, manganese chloride and manganese nitrate.

### Claim 8 (depends on 7)

The process as claimed in claim 7 wherein the manganese ion source used is manganese acetate.

### Claim 9 (depends on 6)

The process as claimed in claim 6 wherein the source of cobalt ions used is selected from the group consisting of cobalt acetate, cobalt chloride and cobalt nitrate.

### Claim 10 (depends on 9)

The process as claimed in claim 9 wherein the cobalt ion source used is cobalt acetate.

### Claim 11 (depends on 5)

The process as claimed in claim 5 wherein the alkali metal salt used is selected from the group consisting of sodium bromide, sodium chloride, potassium bromide, potassium chloride and potassium iodide.

### Claim 12 (depends on 11)

The process as claimed in claim 11 wherein the alkali metal salt used is sodium bromide.

### Claim 13 (depends on 5)

The process as claimed in claim 5 wherein the, porous encapsulant used comprises micro and mesoporous materials selected from the group consisting of aluminosilicate zeolites, aluminophosphates, silica and carbon molecular sieves.

### Claim 14 (depends on 5)

The process as claimed in claim 5 wherein the acid used is glacial acetic acid.

### Claim 15 (depends on 5)

The process as claimed in claim 5 wherein L′ is selected from the group consisting of ClO4−, BF4−, PF6−, and BrO3−.