Synthesis and crystal structure of tris(diethyldithiocarbamato-S,S′)(disulfido-S,S′)niobium(V)

Abstract

The reaction of [Nb^VO(S₂CNEt₂)₃] with boron sulfide was investigated under a variety of conditions. The major product in all cases was yellow [Nb^VS(S₂CNEt₂)₃]1. In dichloromethane at room temperature, orange [Nb^V(S₂)(S₂CNEt₂)₃]2 and orange-brown [Nb^IV₂(µ-S₂)₂(S₂CNEt₂)₄]3 were also formed. At higher temperatures the same products were formed but a higher proportion of 1 was observed. Crystals of 2·0.5CH₂Cl₂ were monoclinic, space group C2/c with a= 16.360(2), b= 10.959(1), c = 30.637(3)Å, β= 92.34(1)° and Z= 8. The structure was refined to final R= 0.034 for 2310 reflections with I 2.5σ(I). The eight-co-ordinate complex exhibits an mmmm dodecahedral structure analogous to that of its tantalum counterpart.