Structure–redox potential relations of metal complexes. Part 1. Organodiazenido-complexes of molybdenum: neighbouring-group influence on redox potential

Abstract

Aryldiazenido-complexes, [Mo(N₂C₆H₄X)(S₂CNMe₂)₃](X = a range of ortho-, meta-, and para-substituents), undergo reversible one-electron oxidation to stable cations in non-aqueous electrolytes at platinum or vitreous carbon electrodes. E.s.r. spectra indicate that the highest occupied molecular orbital (h.o.m.o.) is essentially metal in character, and plots of E_½ against Hammett constants show that the influence of X on the h.o.m.o. via the –NN– linkage is primarily through an inductive rather than a resonance mechanism.