Dioxygenation Reaction of a Cobalt-Nitrosyl: Putative Formation of a Cobalt–Peroxynitrite via a CoIII(NO)(O2–) Intermediate

2017/11/13 by Kuldeep Gogoi, Soumen Saha, Baishakhi Mondal +3 · 4 citations
Chemistry · Medicine · Materials Science · #Metal-Catalyzed Oxygenation Mechanisms #Nitric Oxide and Endothelin Effects #Porphyrin and Phthalocyanine Chemistry

paper · doi:10.1021/acs.inorgchem.7b01673

Abstract

A cobalt-nitrosyl complex, [(BPI)Co(NO)(OAc)], 1 BPI = 1,3-bis(2′-pyridylimino)isoindol was prepared and characterized. Structural characterization revealed that the cobalt center has a distorted square pyramidal geometry with the NO group coordinated from the apical position in a bent fashion. The addition of dioxygen (O 2 ) to the dichloromethane solution of complex 1 resulted in the formation of nitro complex, [(BPI)Co(NO 2 )(OAc)], 2 . It was characterized structurally. Kinetic studies suggested the involvement of an associative mechanism. FT-IR spectroscopic studies suggested the formation of the intermediate 1a [(BPI)Co III (NO)(O 2 – )(OAc)] in the reaction. The intermediate 1a decomposed to complex 2 via a presumed peroxynitrite intermediate which was implicated by its characteristic phenol ring nitration reaction.

Citations

• ORTEP-3 for Windows - a version ofORTEP-III with a Graphical User Interface (GUI)
• Chemistry of Peroxynitrites as Compared to Peroxynitrates

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