Reductive Coupling of Nitric Oxide by Cu(I): Stepwise Formation of Mono- and Dinitrosyl Species En Route to a Cupric Hyponitrite Intermediate.

ABSTRACT: Transition-metal-mediated reductive coupling of nitric oxide (NO_(g)) to nitrous oxide (N₂O_(g)) has significance across the fields of industrial chemistry, biochemistry, medicine, and environmental health. Herein, we elucidate a density functional theory (DFT)-supplemented mechanism of NO_(g) reductive coupling at a copper-ion center, [(tmpa)Cu^I(MeCN)]⁺ (1) {tmpa = tris(2-pyridylmethyl)amine}. At -110 °C in EtOH (<-90 °C in MeOH), exposing 1 to NO_(g) leads to a new binuclear hyponitrite intermediate [{(tmpa)Cu^II}₂(μ-N₂O₂^2-)]²⁺ (2), exhibiting temperature-dependent irreversible isomerization to the previously characterized κ^2<

SUBMITTER: Bhadra M 

PROVIDER: S-EPMC10122266 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature