Preparation and Molecular Structures of [Co(S2O-S,S′)(Me2PCH2CH2PMe2)2]ClO4 and [Co(S2PMe2)2(Me2PCH2CH2PMe2)]BF4

Abstract

Abstract The reaction of elemental sulfur S8 with [Co(dmpe)2](BF4)2 in a mixture of methanol and benzene gave a novel S,S′-coordinated disulfur oxide cobalt(III) complex, [Co(S2O-S,S′)(dmpe)2]ClO4 (1), and a dimethyldithiophosphinato complex, [Co(S2PMe2)2(dmpe)]BF4 (2). The molecular structures of these complexes were determined by X-ray structure analyses. Crystal data for complex 1: monoclinic, P21/n, a = 14.702(3), b = 11.645(1), c = 14.333(2) Å, β = 109.90(2)°, V = 2307.4(2) Å3, Dx = 1.55, Dm = 1.54(3) g cm−3, Z = 4, R = 0.039 for 4542 reflections. Crystal data for complex 2: orthorhombic, Pnc2, a = 13.383(3), b = 12.333(2), c = 13.742(3) Å, V = 2268.1(8) Å3, Dx = 1.60, Dm = 1.59(2) g cm−3, Z = 4, R = 0.075 for 2060 reflections. The central sulfur atom of the S–S–O group in complex 1 exerts a larger trans influence than does the terminal sulfur.