Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2022 Mar 10

PMID 35267236

Authors

Matus Stredansky

Stefania Moro

Manuel Corva

Henning Sturmeit

Valentin Mischke

David Janas

Iulia Cojocariu

Matteo Jugovac

Albano Cossaro

Alberto Verdini

Luca Floreano

Zhijing Feng

Alessandro Sala

Giovanni Comelli

Andreas Windischbacher

Peter Puschnig

Chantal Hohner

Miroslav Kettner

Jorg Libuda

Mirko Cinchetti

Claus Michael Schneider

Vitaliy Feyer

Erik Vesselli

Giovanni Zamborlini

Affiliations

Soon will be listed here.

Abstract

Uncommon metal oxidation states in porphyrinoid cofactors are responsible for the activity of many enzymes. The F and P450nor co-factors, with their reduced Ni - and Fe -containing tetrapyrrolic cores, are prototypical examples of biological systems involved in methane formation and in the reduction of nitric oxide, respectively. Herein, using a comprehensive range of experimental and theoretical methods, we raise evidence that nickel tetraphenyl porphyrins deposited in vacuo on a copper surface are reactive towards nitric oxide disproportionation at room temperature. The interpretation of the measurements is far from being straightforward due to the high reactivity of the different nitrogen oxides species (eventually present in the residual gas background) and of the possible reaction intermediates. The picture is detailed in order to disentangle the challenging complexity of the system, where even a small fraction of contamination can change the scenario.

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