Hydrosulfide Oxidation at a Molybdenum Tetrasulfido Complex.

Hydrogen sulfide (HS) is an important biological signaling molecule and one of three established gasotransmitters. Upon oxidation, HS can form reactive sulfur species (RSS) that play a central role in protein persulfidation. Here we report that a molybdenum tetrasulfide can react directly with hydrosulfide to form polysulfides and oxidize the Mo center. Specifically, [NBu][TpMoS(S)] reacts with 2 equiv of [NBu][SH] to form [NBu][TpMoS]. Trapping experiments with BnBr confirm the formation of polysulfides, as evidenced by the direct trapping of BnS. This work demonstrates new reaction pathways for HS oxidation and RSS generation from metal-bound polysulfides that will increase our understanding of the potential roles that metals play in signaling processes.