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-N(3), 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.