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Thiol and H₂S-Mediated NO Generation from Nitrate at Copper(II)

Pokhraj Ghosh^1,2, Molly Stauffer^1,2, Md Estak Ahmed^1,2

¹Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, United States.

Journal of the American Chemical Society

|May 24, 2023

Abstract:

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 [Cl₂NN_F6]Cu(κ²-O₂NO) engages in O-atom transfer with various thiols (RSH) to form the corresponding copper(II) nitrite [Cu^II](κ²-O₂N) 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 H₂S also reduces nitrate at copper(II) to generate NO, providing a lens into NO₃^-/H₂S crosstalk. The interaction of thiols with nitrate at copper(II) releases a cascade of N- and S-based signaling molecules in biology.

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