Issue 24, 2023

Acid-induced conversion of nitrite to nitric oxide at the copper(ii) center: a new catalytic pathway

Abstract

Acid-induced reduction of nitrites (NO2) to nitric oxide (NO) at Cu/Fe centers is one of the key steps in the nitrogen cycle and serves as an essential path to NO generation. In this study, we report the acid-catalysed conversion of NO2 to NO at the CuII centers in CuII-nitrito complexes, [(Me2BPMEN)CuII(NO2)]+ (1) and [(H2BPMEN)CuII(NO2)]+ (2). Both the CuII-NO2 complexes showed the formation of NO(g) along with H2O2 when reacted with one equivalent acid (H+) via the N–O bond homolysis of the presumed CuII-nitrous acid ([Cu-ONOH]2+) intermediate. However, the H2O2 amount decreased with time or an increase in H+ and completely disappeared when H+ was more than about two equivalents accompanied by the generation of H2O. We detected the released NO(g) by using headspace gas chromatography/mass spectrometry; moreover, the NO(g) evolution was confirmed by the formation of a significant amount of {CoNO}8, [(12-TMC)Co(NO)]2+ up to (90 ± 5%) in the above reactions. Mechanistic investigations using 15N-labeled-15NO2 and 18O-labeled-16O14N18O revealed that the N-atom in NO is derived from the 18ONO ligand, which was further confirmed by the detection of 15NO and N18O gas in headspace gas chromatography/mass spectrometry. We also monitored and characterized the formation of H2O2 (one equivalent of H+) and H2O (two equivalents of H+) and the results describe the rationale behind biological NO2 reduction reactions generating NO along with H2O. We observed more than 90% recovery of (1) after 10 catalytic cycles of NO(g) generation.

Graphical abstract: Acid-induced conversion of nitrite to nitric oxide at the copper(ii) center: a new catalytic pathway

Supplementary files

Article information

Article type
Research Article
Submitted
01 Sep 2023
Accepted
24 Oct 2023
First published
08 Nov 2023

Inorg. Chem. Front., 2023,10, 7285-7295

Acid-induced conversion of nitrite to nitric oxide at the copper(II) center: a new catalytic pathway

P. Bhardwaj, Kulbir, T. Devi and P. Kumar, Inorg. Chem. Front., 2023, 10, 7285 DOI: 10.1039/D3QI01637D

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