Unexpected formation of anti-1,2-W2(SBut)2(NMe2)4 in the thiolysis of gauche-1,2-W2Cp2(NMe2)4 and W2COT(NMe2)4 with ButSH

Thiolysis of W2Cp2(NMe2)4 and W2COT(NMe2)4 with excess ButSH leads to cleavage of the respective carbocyclic rings from the ditungsten center and formation of the compound anti-1,2-W2(SBut)2(NMe2)4 which was characterized via a single-crystal X-ray diffraction study. This product was found to be isostructural with its dimolybdenum analogue. The compound is a prototypical ethane-like dimer having a Wtriple bond; length of mdashW bond distance of 2.3011(3) Å and thiolate ligands in an anti configuration about the Wtriple bond; length of mdashW bond. The thiolysis reactions for both dimethylamide precursors are contrasted with the results of their respective alcoholysis reactions.