Cyclic voltammetry, potential-dependent chronoamperometry and controlled potential electrolysis have been used to investigate the redox reactions which the nickel-triphenylphosphine system undergoes in acetonitrile solution in the presence of the activated olefin acrylonitrile. For the reduction of Ni(II) electrochemically generated in this medium, a mechanism is proposed which is consistent with the data. This species undergoes an irreversible two-electron reduction giving the corresponding Ni(0) complex which reacts quickly with the olefin. In this last homogeneous redox reaction an unusual and not previously reported olefin-Ni(I) derivative is obtained. The geometric configuration of such an organometallic compound has been then inferred on the basis of near-infrared and ESR spectra. © 1983 Elsevier Sequoia S.A.
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