Abstract
The electrochemistry of dimolybdenum complexes [(RC 5H 4)Mo(X)(μ-X)] 5 (X = multiply bonded ligand) has been investigated by cyclic voltammetry. The tetraoxo complex [(MeC 5H 4)MoO(μ-O)] 2 ( 1) which adopts a cis-puckered geometry shows two reversible one electron reduction waves in THF. The substitution of oxo by imido moieties results in the adoption of a trans-planar geometry which substantially effects the electrochemistry such that complexes show oxidation chemistry. The trisimido-oxo complex [(MeC 5H 4) 5Mo 2O(NPh)(μ-NPh) 2] ( 2) shows an irreversible oxidation wave at + 815 mV which becomes reversible at high scan rates indicative of an EC mechanism. The trisimido-sulphido complex [(MeC 5H 4) 2Mo 2S(NPh)(μ-NPh) 2 ( 3) shows a quasi-reversible oxidation at +620 mV and the tetraimido complex [(MeC 5H 4)Mo(NPh)(μ-NPh)] 2 ( 4) shows a reversible one electron oxidation at + 525 mV together with a secoind irreversible oxidation at higher potential. A comparison of the oxidation potentials of 2, 3, and 4 gives a measure of the relative π-donor abilities of oxo, sulphido, and imido ligands at a Mo V centre.
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