Abstract: | Vanadium chemistry is of interest due its biological relevance and medical applications. In particular, the interactions of high‐valent vanadium ions with sulfur‐containing biologically important molecules, such as cysteine and glutathione, might be related to the redox conversion of vanadium in ascidians, the function of amavadin (a vanadium‐containing anion) and the antidiabetic behaviour of vanadium compounds. A mechanistic understanding of these aspects is important. In an effort to investigate high‐valent vanadium–sulfur chemistry, we have synthesized and characterized the non‐oxo divanadium(IV) complex salt tetraphenylphosphonium tri‐μ‐<!?tlsb=‐0.11pt>methanolato‐κ6O:O‐bis({tris2‐sulfanidyl‐3‐(trimethylsilyl)phenyl]phosphane‐κ4P,S,S′,S′′}vanadium(IV)) methanol disolvate, (C24H20P)VIV2(μ‐OCH3)3(C27H36PS3)2]·2CH3OH. Two VIV metal centres are bridged by three methanolate ligands, giving a C2‐symmetric V2(μ‐OMe)3 core structure. Each VIV centre adopts a monocapped trigonal antiprismatic geometry, with the P atom situated in the capping position and the three S atoms and three O atoms forming two triangular faces of the trigonal antiprism. The magnetic data indicate a paramagnetic nature of the salt, with an S = 1 spin state. |