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.