ISSN:
1572-8862
Keywords:
Palladium
;
carbene
;
oxidation
;
phosphonate
;
carboxylate
Source:
Springer Online Journal Archives 1860-2000
Topics:
Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
,
Physics
Notes:
Abstract 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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00702748
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