Nitrite Reduction by Trinuclear Copper Pyrazolate Complexes: An Example of a Catalytic, Synthetic Polynuclear NO Releasing System

Kaige Shi; Logesh Mathivathanan; Athanassios K Boudalis; Philippe Turek; Indranil Chakraborty; Raphael G Raptis

doi:10.1021/acs.inorgchem.9b00748

Nitrite Reduction by Trinuclear Copper Pyrazolate Complexes: An Example of a Catalytic, Synthetic Polynuclear NO Releasing System

Inorg Chem. 2019 Jun 3;58(11):7537-7544. doi: 10.1021/acs.inorgchem.9b00748. Epub 2019 May 15.

Authors

Kaige Shi¹, Logesh Mathivathanan¹, Athanassios K Boudalis², Philippe Turek², Indranil Chakraborty¹, Raphael G Raptis¹

Affiliations

¹ Department of Chemistry and Biochemistry and Biomolecular Sciences Institute , Florida International University , 11200 SW Eighth Street , Miami , Florida 33199 , United States.
² Institut de Chimie UMR 7177/Université de Strasbourg 4 , rue Blaise Pascal/CS 90032 , F-67081 Strasbourg CEDEX, France.

PMID: 31091082
DOI: 10.1021/acs.inorgchem.9b00748

Abstract

Two trinuclear Cu^II pyrazolato complexes with a Cu₃(μ₃-E)-core (E = O^2- or OH^-) and terminal nitrite ligands in two coordination modes were characterized crystallographically, spectroscopically, and electrochemically. One-electron oxidation of the μ₃-O species produces a delocalized, mixed-valent, formally Cu^II₂Cu^III-nitrite, but no nitrate. In contrast, under reducing conditions-addition of PhSH as an electron and proton donor-both complexes mediate the reduction of nitrite, releasing NO.