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

W2COT(NMe2)4 and 1,2-W2Cp2(NMe2)4 undergo thiolysis with excess ButSH to produce the known thiolate compound anti-1,2-W2(SBut)2(NMe2)4. The solid state structure of the thiolate product was determined and it was shown to be isostructural with the Mo analogue. The preferential W-C activation observed during thiolysis is contrasted with the alcoholysis reactions of the same precursors.