Electrochemical oxidation of organometallic complexes. Carbene and Lewis base complexes of chromium, molybdenum, and tungsten carbonyls
- 1 January 1973
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 17,p. 1743-1747
- https://doi.org/10.1039/dt9730001743
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, E½, is influenced by each of the variables M, L(or LL), n, X, and Y. The order of E½-values follows closely the apparent π-acceptor/σ-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 E½, especially where bidentate ligands are present. The oxidation potentials are related to synthetic chemistry in these systems.Keywords
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