Thiolateisocyanide complexes of molybdenum(II) and tungsten(II): crystal structures of cis-[Mo(SC6H2Pri3-2,4,6)2(CNMe)4], cis-[Mo(SC6H2Pri3-2,4,6)2(CNBut)4] and cis-[W(SC6H2Pri3-2,4,6)2(CNMe)4], and anodically induced isomerisation studies

Abstract

Reaction of [MH(SC₆H₂Prⁱ₃-2,4,6)₃(PMe₂Ph)₂] (M = Mo or W) or [MoH(SC₆H₂Prⁱ₃-2,4,6)₃(PMePh₂)] with RNC (R = Me or Bu^t) gave the complexes cis-[M(SC₆H₂Prⁱ₃-2,4,6)₂(CNR)₄] 1 (M = Mo, R = Me or Bu^t; M = W, R = Me), which have been shown to have distorted octahedral geometry by X-ray crystallography. Spectroscopic data for 1 are also described. At –50 °C in CH₂Cl₂ solution the complexes cis-[Mo(SC₆H₂Prⁱ₃-2,4,6)₂(CNR)₄] (R = Me or Bu^t) undergo an anodically induced isomerisation according to an electrochemical–chemical square-type mechanism for which rate and equilibrium constants have been estimated by digital simulation of cyclic voltammetric data.