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. D(x)=1.55, D(m)=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, D(x)=1.60, D(m)=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.
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