Journal of Cluster Science

, Volume 3, Issue 4, pp 411–421 | Cite as

Oxidation of bridging groups by carboxylate coordinated ligands in palladium clusters

  • Ilya I. Moiseev
  • Tatiana A. Stromnova
  • Irina N. Busygina
  • Natalya Yu. Tihonova
  • Natalya Yu. Kozitsyna
  • Arkady M. Ellern
  • Mikhail Yu. Antipin
  • Yury T. Struchkov
Proceedings Of The US-Italy International Conference On Organic Chemistry At Clusters And Surfaces, Piemonte, Italy (July 26–31, 1992)—Part II Of III
Received:

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.

Key words

Palladium carbene oxidation phosphonate carboxylate 
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Copyright information

© Plenum Publishing Corporation 1992

Authors and Affiliations

  • Ilya I. Moiseev
    • 1
  • Tatiana A. Stromnova
    • 1
  • Irina N. Busygina
    • 1
  • Natalya Yu. Tihonova
    • 1
  • Natalya Yu. Kozitsyna
    • 1
  • Arkady M. Ellern
    • 1
  • Mikhail Yu. Antipin
    • 2
  • Yury T. Struchkov
    • 2
  1. 1.N. S. Kurnakov Institute of General and Inorganic ChemistryRussian Academy of SciencesMoscowRussia
  2. 2.A. N. Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussia

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