Oxidation of bridging groups by carboxylate coordinated ligands in palladium clusters |
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| Authors: | Ilya I. Moiseev Tatiana A. Stromnova Irina N. Busygina Natalya Yu. Tihonova Natalya Yu. Kozitsyna Arkady M. Ellern Mikhail Yu. Antipin Yury T. Struchkov |
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| Affiliation: | (1) N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 117907 Moscow, Russia;(2) A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 127334 Moscow, Russia |
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| Abstract: | Thermolysis of tetranuclear palladium clusters Pd4( -Q)4 Pd4(-Q)4(-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(-O2PPh2)(C6H5)(PPh3)]2, has been resolved by X-ray analysis. |
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| Keywords: | Palladium carbene oxidation phosphonate carboxylate |
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