Thiol and H 2 S-Mediated NO Generation from Nitrate at Copper(II).

Reduction of nitrate is an essential, yet challenging chemical task required to manage this relatively inert oxoanion in the environment and biology. We show that thiols, ubiquitous reductants in biology, convert nitrate to nitric oxide at a Cu(II) center under mild conditions. The β-diketiminato complex [Cl 2 NN F6 ]Cu(κ 2 -O 2 NO) engages in O-atom transfer with various thiols (RSH) to form the corresponding copper(II) nitrite [Cu II ](κ 2 -O 2 N) and sulfenic acid (RSOH). The copper(II) nitrite further reacts with RSH to give S -nitrosothiols RSNO and [Cu II ] 2 (μ-OH) 2 en route to NO formation via [Cu II ]-SR intermediates. The gasotransmitter H 2 S also reduces nitrate at copper(II) to generate NO, providing a lens into NO 3 - /H 2 S crosstalk. The interaction of thiols with nitrate at copper(II) releases a cascade of N- and S-based signaling molecules in biology.