Abstract
A series of (CO)5ML (M = Cr, Mo, W) complexes, where L is a phosphonium-substituted phenylisocyanide ligand of the type o-R3PCH2C6H4NC [PR3 =PMe3, PPh2Bz, PPh3 ], a carbene-type (CO)5M=[o-CN(H)C6H4C(PR3)], indole-type (CO)5M-[o-NC(H)C(PR3)(C6H4)] or protonated indole-type (CO)5M-[o-N(H)C(H)C(PR3)(C6H4)] species, have been studied by cyclic voltammetry and controlled potential electrolysis in aprotic media. They undergo a single-electron (reversible or irreversible) anodic wave and their oxidation potential has been applied to estimate the PL and EL ligand parameters for the isocyanide and derived ligands which, according to their net electron donor ability, can then be ordered as follows: indoles > carbenes > protonated carbenes or protonated indoles > isocyanides. For the metal-centres {M(CO)5} (M = Mo or W), the electrochemical parameter β (polarisability) has also been estimated.
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