Denitrification
The reduction of nitric oxide (NO) to nitrous oxide (N2O) by nitric oxide reductase (NOR) is an important component of the global nitrogen cycle; however, the mechanism of reduction is not well understood. Here, synthetic chemistry can play an important role. We recently synthesized a unique Nickel(II) nitroxyl complex, [Ni(bipy)2(NO)][PF6], which may help in our understanding of NOR. On standing in acetonitrile, this complex furnishes the NO coupled product, [Ni(κ2-O2N2)(bipy)], in moderate yield. Subsequent addition of 2 equiv of acetylacetone (H(acac)) to [Ni(κ2-O2N2)(bipy)] results in formation of [Ni(acac)2(bipy)], N2O and H2O. Preliminary mechanistic studies suggest that the N–N bond in [Ni(κ2-O2N2)(bipy)] is formed via a bimetallic coupling reaction of two nitroxyl (NO–) ligands, a finding which may have implications on our understanding of nitric oxide reductase.
Publications
- Synthesis of a "Masked" Terminal Nickel(II) Sulfide by Reductive Deprotection and its Reaction with Nitrous Oxide
- Understanding the role of hyponitrite in nitric oxide reduction
- Mechanistic insights into the formation of N<sub>2</sub>O by a nickel nitrosyl complex
- Nitric oxide release from a nickel nitrosyl complex induced by one-electron oxidation