ELECTROCHEMICAL OXIDATION OF ORGANOMETALLIC COMPLEXES - CARBENE AND LEWIS BASE COMPLEXES OF CHROMIUM, MOLYBDENUM, AND TUNGSTEN CARBONYLS Academic Article uri icon

abstract

  • Tha oxidative one-electron transfer reactions of a wide variety of Group VI metal carbonyl derivatives have been detected by voltammetry. The compounds studied are of the type M(CO)6 - nLn or M(CO)6 - 2n(LL)n (M = Cr, Mo, W; L = monodentate Lewis base, n = 1 or 2; LL = bidentate Lewis base, n = 1 or 2) and carbene complexes of the type M(CO)5C(X)Y. The value of the potential, E1/2;, is influenced by each of the variables M, L(or LL), n, X, and Y. The order of E1/2;-values follows closely the apparent -acceptor/-donor ratio of the ligand, but comparison with the results of molecular orbital calculations suggests that the influence of L (or of {C(X)Y}) upon the redox orbital is indirect. Steric effects are shown to influence the value of E1/2;, especially where bidentate ligands are present. The oxidation potentials are related to synthetic chemistry in these systems.

published proceedings

  • JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS

author list (cited authors)

  • LLOYD, M. K., MCCLEVER, J. A., ORCHARD, D. G., CONNOR, J. A., HALL, M. B., HILLIER, I. H., JONES, E. M., & MCEWEN, G. K.

citation count

  • 66

complete list of authors

  • LLOYD, MK||MCCLEVER, JA||ORCHARD, DG||CONNOR, JA||HALL, MB||HILLIER, IH||JONES, EM||MCEWEN, GK

publication date

  • December 1973