Preparation and Characterization of a Diamagnetic Sulfido-Bridged Divanadium Amide Complex

Reaction of [(Me(3)Si)(2)N](2)VCl(THF) with S(8) led to the formation of the dinuclear and diamagnetic complex {[(Me(3)Si)(2)N](2)V}(2)(&mgr;-S)(2) (1), whose connectivity was elucidated by an X-ray crystal structure. Ab initio theoretical calculations carried out on both complex 1 and the isostructural oxo-bridged dimer indicated a determinant participation of the bridging atoms in the formation of V-V bonds. Crystal data for 1 are as follows: C(24)H(72)N(4)Si(8)V(2)S(2), fw 807.54, monoclinic P2(1)/c, a = 9.1386(2) Å, b = 14.5955(3) Å, c = 34.8578(6) Å, beta = 95.744(1) degrees, V = 4626.1(1) Å(3), Z = 4, T = -153 degrees C.