PREPARATION AND MOLECULAR-STRUCTURES OF [CO(S2O-S,S')(ME2PCH2CH2PME2)2]CLO4 AND [CO(S2PME2)2(ME2PCH2CH2PME2)]BF4

The reaction of elemental sulfur S8 with [Co(dmpe)2](BF4)2 in a mixtur e of methanol and benzene gave a novel SS-coordinated disulfur oxide c obalt(III) complex, [CO(S2O-S,S')(dmpe)2]ClO4 (1), and a dimethyldithi ophosphinato complex, [CO(S2PMe2)2(dmpe)]BF4 (2). The molecular struct ures of these complexes were determined by X-ray structure analyses. C rystal data for complex 1: monoclinic, P2(1)/n, a = 14.702(3), b=11.64 5 (1), c=14.333(2) angstrom, beta=109.90(2)-degrees, V=2307.4(2) angst rom3, D(x)=1.55, D(m)=1.54(3) g cm-3, Z=4, R=0.039 for 4542 reflection s. Crystal data for complex 2: orthorhombic, Pnc2, a=13.383(3), b=12.3 33(2), c=13.742(3) angstrom, V=2268.1(8) angstrom3, D(x)=1.60, D(m)=1. 59(2) g cm-3, Z=4, R=0.075 for 2060 reflections. The central sulfur at om of the S-S-O group in complex 1 exerts a larger trans influence tha n does the terminal sulfur.