Synthesis of a Vanadium(III) Tris(arylthiolato) Complex and Its Reactions with Azide and Azo Compounds: Formation of a Sulfenamide Complex via Cleavage of an Azo NN Bond

The tris(arylthiolate) vanadium(III) complex (1) has been synthesized in good yield. This complex is found to undergo CH activation across a V−S bond in the presence of TMEDA to give a cyclometalated species along with free arylthiol. Complex 1 behaves as a two-electron reductant toward Ad−N3, yielding an imide complex. Treatment of 1 with azobenzene produces an imide−sulfenamide compound, in which an azo NN bond cleavage takes place concomitant with formation of a VN and an SN bond.