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Updated: Jan 8, 2026
Measuring Nitrite and Nitrate, Metabolites in the Nitric Oxide Pathway, in Biological Materials using the Chemiluminescence Method
Published on: December 25, 2016
Reduction of Nitrite to Nitric Oxide by Tetranuclear Iron(II)-Polychalcogenides: Direct Reduction by Iron(II) vs the
Amit Mandal1, Sayan Atta1, Amit Majumdar1
1School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Kolkata 700032, West Bengal, India.
Abstract:
The complexes, [Fe2(HPTP)(EPh)2]1+ (E = S, 2a; Se, 2b), [Fe4(HPTP)2(S3)(S6)]2+ (3) and [Fe4(HPTP)2(Se3)2]2+ (4), directly reduced nitrite (NO2-) to nitric oxide (NO) and generated the DNICs, [Fe(EPh)2(NO)2]1- and [Fe(E5)(NO)2]1- (E = S, Se), respectively. The complexes, 2a, 2b, 3, and 4, featured oxidation events of the Fe(II) centers at very negative potentials and could mediate the direct reduction (in the absence of protons) of NO2- to NO, where the second "oxo" of NO2- was stabilized by the formation of a tetrairon(III) complex, [Fe4(HPTP)2(μ-O)3(μ-OH)]3+. The nucleophilic attack of NO2- on the "neutral" chalcogen atoms of the coordinated polychalcogenide chains in 3 or 4, however, also generated perthionitrite (SSNO-) or its selenium analogue and NO, which, in turn, produced [Fe(E5)(NO)2]1- (E = S, Se). Critical analysis of the experimental results, which includes X-ray structural, EPR and IR spectroscopic, and mass spectrometric investigations, including 15N isotope labeling studies, and comparison with literature reports indicated that the direct reduction of NO2- to NO by the Fe(II) centers in 3 and 4 was the major reaction pathway while the nucleophilic attack of NO2- on the "neutral" chalcogen atoms leading to the generation of [Fe(E5)(NO)2]1- (E = S, Se) was only a minor pathway.
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