The dual roles of a V(III) centre for substrate binding and oxygen atom abstraction; nitrite reduction mediated by a V(III) complex.

A V(iii) complex bearing a tris(thiolato)phoshine derivative mediates the reduction of nitrite without the assistance of external protons or oxophilic substrates. The metal site plays dual roles for nitrite binding and deoxygenation. The reaction is monitored by spectroscopy combined with isotopic labeling experiments. The formed product, a {VNO}4 species, is isolated and characterized.