Photochemistry of Tetrasulfido Complexes of Molybdenum(VI), Tungsten(VI), Vanadium(V) and Rhenium(VII)

Abstract

The tetrasulfido complexes [MoS4]2-, [WS4]2-, [VS4]3-, and [ReS4]- photolyze in solution in the presence of air according to the stoichiometry [MS4]n- + 02 -> [M02S2]n- + S2. The diatomic sulfur can be scavenged by norbornadiene or tetramerizes to yield stable S8. Quantum yields are strongly wavelength-dependent. For all complexes the reactive excited states are of the ligand to metal charge transfer type.