Oxidation of bridging groups by carboxylate coordinated ligands in palladium clusters

Autor: I. N. Busygina, Ilya I. Moiseev, Natalya Yu. Kozitsyna, Yury T. Struchkov, Mikhail Yu. Antipin, Natalya Yu. Tihonova, Arkady M. Ellern, Tatiana A. Stromnova
Rok vydání: 1992
Předmět:
Zdroj: Journal of Cluster Science. 3:411-421
ISSN: 1572-8862
1040-7278
DOI: 10.1007/bf00702748
Popis: Thermolysis of tetranuclear palladium clusters Pd4(μ-Q)4 Pd4(μ-Q)4(μ-O2CR)4 (Q=CPh2 or CO;R=Me, CMe3, Ph, CH2Cl or CF3) has been found to involve innersphere oxidation of carbene or carbonyl ligands during which an oxygen atom transfer occurs from the carboxylate group to the carbene or carbonyl ligand. The thermolysis of the carbonyl clusters gives rise to the products of CO2 insertion into the C–H bond of benzene or toluene used as solvents forming benzoic acid from benzene and a mixture of phenylacetic and toluic acids from toluene. The reaction of [Pd(OAc)2(PPh3)]2 with HCO2H includes the transfer of an O atom from formate ligand to the P atom and cleavage of the P-Ph bond accompanied by transfer of the Ph group from PPh3 ligand to the palladium atom. The structure of the complex formed, [Pd(μ-O2PPh2)(C6H5)(PPh3)]2, has been resolved by X-ray analysis.
Databáze: OpenAIRE
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