Mechanism of O-Atom Transfer from Nitrite: Nitric Oxide Release at Copper(II)

Overview

Journal Inorg Chem

Specialty Chemistry

Date 2021 Jun 29

PMID 34184870

Citations 3

Authors

Molly Stauffer

Zeinab Sakhaei

Christine Greene

Pokhraj Ghosh

Jeffery A Bertke

Timothy H Warren

Affiliations

Soon will be listed here.

Abstract

Nitric oxide (NO) is a key signaling molecule in health and disease. While nitrite acts as a reservoir of NO activity, mechanisms for NO release require further understanding. A series of electronically varied β-diketiminatocopper(II) nitrite complexes [Cu](κ-ON) react with a range of electronically tuned triarylphosphines PAr that release NO with the formation of O═PAr. Second-order rate constants are largest for electron-poor copper(II) nitrite and electron-rich phosphine pairs. Computational analysis reveals a transition-state structure energetically matched with experimentally determined activation barriers. The production of NO follows a pathway that involves nitrite isomerization at Cu from κ-ON to κ-NO followed by O-atom transfer (OAT) to form O═PAr and [Cu]-NO that releases NO upon PAr binding at Cu to form [Cu]-PAr. These findings illustrate important mechanistic considerations involved in NO formation from nitrite via OAT.

Citing Articles

Synthetically Reversible, Proton-Mediated Nitrite N-O Bond Cleavage at a Dicopper Site.

Martinez Fernandez J, Haji Seyed Javadi A, Teat S, Cundari T, Don Tilley T J Am Chem Soc. 2024; 146(50):34962-34969.

PMID: 39655620 PMC: 11664590. DOI: 10.1021/jacs.4c14642.

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

Ghosh P, Stauffer M, Ahmed M, Bertke J, Staples R, Warren T J Am Chem Soc. 2023; 145(22):12007-12012.

PMID: 37224264 PMC: 10367543. DOI: 10.1021/jacs.3c00394.

NO Coupling at Copper to -Hyponitrite: NO Formation via Protonation and H-Atom Transfer.

Ghosh P, Stauffer M, Hosseininasab V, Kundu S, Bertke J, Cundari T J Am Chem Soc. 2022; 144(33):15093-15099.

PMID: 35948086 PMC: 9536194. DOI: 10.1021/jacs.2c04033.

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