Synthetic route to vanadium(III) dichalcogenidophosphinate complexes, V(S2PPh2)3 and V(Se2PPh2)3: A spectroscopic and structural comparative study with analogous complexes of chromium(III), Cr(E2PPh2)3 (E=S, Se)

Abstract

AbstractAddition of the potassium dichalcogenidodiphenylphosphinate salts, KE2PPh2 (E=S, Se), to either the THF solvate of vanadium(III) chloride or unsolvated chromium(III) chloride results in rapid ligand substitution and the formation of a series of closely‐related trivalent, neutral mononuclear complexes, M(E2PPh2)3 (M=V, Cr; E=S, Se), isolated in modest to good yield. The metal dichalcogenidophosphinate complexes reported herein were characterized by IR, UV‐vis, and 1H NMR spectroscopies, and their solid‐state molecular structures were determined by single‐crystal X‐ray crystallography. Importantly, the comparative analysis includes the structural and spectroscopic studies of two rare V(III) dithio‐ and diseleno‐phosphinate VE6 cores, as well as, two previously known CrE6 analogues. In the solid‐state the title complexes exhibit trigonal distortion from octahedral with torsion angles ranging from 43(2) to 50.3(6)° and structural parameters consistent with ligation of progressively ‘softer’ chalcogen‐donors.