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.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
I. I. Moiseev,Soviet Sci. Rev., Chemistry Reviews, Sect. B.4 (Harwood Acad. Publ., London, 1982), pp. 139–206.
T. A. Stromnova, I. N. Busygina, N. Yu. Tihonova, and I. I. Moiseev (1991).Mendeleev Commun. 2, 58.
N. Yu. Kozitsyna, A. M. Ellern, M. Yu. Antipin, Yu. T. Struchkov, and I. I. Moiseev (1991).Mendeleev Commun. 3, 92.
G. R. John, B. F. G. Johnson, J. Lewis, W. J. H. Nelson, and M. McPartlin (1979).J. Organometal. Chem. 171, C14.
D. H. Farrar, B. F. G. Johnson, J. Lewis, P. R. Raithby, and M. J. Rosales (1982).J. Chem. Soc. Dalton Trans. 2051.
I. I. Moiseev, T. A. Stromnova, M. N. Vargaftik, G. Ya. Mazo, L. G. Kuz'mina, and Yu. T. Struchkov (1978).J. Chem. Soc. Chem. Commun. 27.
T. A. Stromnova, M. N. Vargaftik, and I. I. Moiseev (1983).J. Organometal. Chem. 252, 113.
T. A. Stromnova, I. N. Busygina, D. I. Kochubey, and I. I. Moiseev (1991).Mendeleev Commun. 1.
S. R. Heller and W. A. Milne (1978). EPA/NIH Spectral Data. Washington.
A. S. Berenblyum, A. G. Kniznik, S. L. Mund, and I. I. Moiseev (1982).J. Organomet. Chem. 234, 219.
T. I. Bakunina, S. V. Zinchenko, V. A. Hutoryanskii, O. V. Burlakova, G. V. Ratovskii, and F. K. Shmidt (1990).Metalloorg. Khim. 3, 462 (in Russian).
N. Yu. Kozitsyna and I. I. Moiseev (to be published).
M. B. Hursthouse, O. D. Sloan, P. Thornton, and N. P. C. Walker (1986).Polyhedron 5(9), 1475.
P. E. Garrou (1985).Chem. Rev. 85, 1713.
T. Yamane, K. Kikukawa, M. Takagi, and T. Matsuda (1973).Tetrahedron 29, 955;
K. Kikukawa, M. Takagi, and T. Matsuda (1982).J. Organomet. Chem. 235, 243;
T. Sakakura, T.-A. Kobayashi, T. Hayashi, Y. Kawabata, M. Tanaka, and I. Ogata (1984).J. Organomet. Chem. 267, 171.
A. R. Chakravarty, F. A. Cotton, and D. A. Tocher (1984).J. Am. Chem. Soc. 106, 6409.
W. Beck, M. Keubler, E. Leidl, U. Nagee, and M. Schaal (1981).J. Chem. Soc. Chem. Commun. 446.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Moiseev, I.I., Stromnova, T.A., Busygina, I.N. et al. Oxidation of bridging groups by carboxylate coordinated ligands in palladium clusters. J Clust Sci 3, 411–421 (1992). https://doi.org/10.1007/BF00702748
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00702748