Summary
The kinetics of the oxidative addition of Hg(CN)2 to [Rh(β-diketone)(P(OPh)3)2] in acetone medium were studied. Various β-diketones, with different electronic and steric properties, were used to determine their effect on the rate of the oxidative addition reactions. The structure of the product of the oxidative addition was proposed with the aid of i.r.,1H−,13C− and31P n.m.r. spectra. A product in whichcis addition took place with the CN− and one P(OPh)3 group in the axial positions of an octahedron were proposed. A second order rate law, electronic and steric factors influencing the reaction rate as well as large negative values for the entropy of activation, supported an associative type of mechanism, which probably proceedsvia a cyclic three-centred transition state.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
A. R. Sanger,Can. J. Chem.,62, 822 (1984).
D. M. Adams, D. J. Cook and R. D. W. Kemmitt,J. Chem. Soc. (A), 1067 (1968).
I. N. Nowell and D. R. Russell,Chem. Commun., 817 (1967).
P. R. Brooks and B. L. Shaw,J. Chem. Soc. Dalton Trans., 783 (1973).
R. S. Nyholm and K. Vrieze,J. Chem. Soc., 5337 (1965).
P. I. van Vliet, J. Kuyper and K. Vrieze,J. Organometall. Chem.,122, 99 (1976).
P. D. Brotherton, C. L. Raston, A. H. White and S. B. Wild,J. Chem. Soc. Dalton Trans., 1799 (1976).
J. Kuyper,Inorg. Chem.,17, 1458 (1978).
D. M. Adams, D. J. Cook and R. D. W. Kemmitt,J. Chem. Soc. (A), 1068 (1968).
P. I. van Vliet, M. Kokkes, G. van Koten and K. Vrieze,J. Organometall. Chem.,187, 413 (1980).
P. I. van Vliet, G. van Koten and K. Vrieze,J. Organometall. Chem.,188, 801 (1980).
g. J. van Zyl, G. J. Lamprecht and J. G. Leipoldt,Inorg. Chim. Acta 129, 35 (1987).
G. J. van Zyl, G. J. Lamprecht and J. G. Leipoldt,Inorg. Chim. Acta,143, 223 (1988).
S. S. Basson, J. G. Leipoldt and J. T. Nel,Inorg. Chim. Acta,84, 167 (1984).
R. Ugo, A. Pasini, A. Fusi and S. Cerini,J. Am. Chem. Soc.,94, 7364 (1972).
H. Singer and G. Wilkinson,J. Chem. Soc. (A), 2516 (1968).
K. Nakamoto,Infrared Spectra of Inorganic and Coordination Compounds, Wiley, New York, 1963.
G. J. van Zyl, G. J. Lamprecht and J. G. Leipoldt,Inorg. Chim. Acta,122, 75 (1986).
L. F. Johnson and W. C. Jankowski,Carbon-13 NMR Spectra, Wiley-Interscience, New York, 1972.
A. C. Jesse, M. A. M. Meester, D. J. Stufkens and K. VriezeInorg. Chim. Acta,26, 129 (1978).
A. M. Trzeciak and J. J. Ziólkowski,Inorg. Chim. Acta L267, 64 (1982).
J. E. Huheey,Inorganic Chemistry Principles of Structure and Reactivity, Harper and Row, New York, 1972.
E. M. Miller and B. L. Shaw,J. Chem. Soc., Dalton. Trans., 480 (1974) and references therein.
W. H. Thomson and C. T. Sears,Inorg. Chem.,4, 769 (1977).
J. K. Stille and K. S. Y. Lau,Acc. Chem. Res.,10, 434 (1977).
C. E. Johnson and R. Eisenberg,J. Am. Chem. Soc.,107, 3148 (1985) and references therein.
R. Kuwae, T. Tanaka and K. Kawakami,Bull. Chem. Soc. Jpn,52, 437 (1979).
J. P. Collman and C. T. Sears,Inorg. Chem.,7, 27 (1968).
M. Kubota, G. W. Kiefer, R. M. Ishikawa and K. E. Bencala,Inorg. Chim. Acta,7, 195 (1973).
J. G. Leipoldt, E. C. Steynberg and R. van Eldik,Inorg. Chem.,26, 3068 (1987).
J. G. Leipoldt, G. J. van Zyl, I. M. Potgieter, G. J. Lamprecht and K. G. van Aswegen, to be published.
S. S. Basson, J. G. Leipoldt, A. Roodt and J. A. Venter,Inorg. Chim. Acta,128, 31 (1987).
J. Stary,The Solvent Extraction of Metal Chelates, Pergamon, Oxford, 1964.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
van Zyl, G.J., Lamprecht, G.J. & Leipoldt, J.G. Oxidative addition of mercury(II)cyanide toβ-diketonatobis-(triphenylphosphite)rhodium(I) complexes. Transition Met Chem 15, 170–175 (1990). https://doi.org/10.1007/BF01023910
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/BF01023910