A thermally stable {FeNO}8 complex: properties and biological reactivity of reduced MNO systems

Reduced nitrogen oxide ligands such as NO/HNO or nitroxyl participate in chemistry distinct from nitric oxide (NO). Nitroxyl has been proposed to form at heme centers to generate the Enemark–Feltham designated {FeNO}8 system. The synthesis of a thermally stable {FeNO}8 species namely, [Co(Cp*)2][Fe(LN4)(NO)] (3), housed in a heme-like ligand platform has been achieved by reduction of the corresponding {FeNO}7 complex, [Fe(LN4)(NO)] (1), with decamethylcobaltocene [Co(Cp*)2] in toluene. This complex readily reacts with metMb, resulting in formation of MbNO via reductive nitrosylation by the coordinatedHNO/NO, which can be inhibited with GSH.These results suggest that 3 could serve as a potentialHNOtherapeutic. Spectroscopic, theoretical, and structural comparisons are made to 1 and the {CoNO}8 complex, [Co(LN4)(NO)] (2), an isoelectronic analogue of 3.

Main Author: Papaefthymiou, Georgia C.
Other Authors: Patra, Ashis K., Dube, Koustubh S., Sanders, Brian C., Conradie, Jeanet, Ghosh, Abhik, Harrop, Todd C.
Format: Villanova Faculty Authorship
Language: English
Published: 2012
Online Access: http://ezproxy.villanova.edu/login?url=https://digital.library.villanova.edu/Item/vudl:436500