Reactions of Co(III)-nitrosyl complexes with superoxide and their mechanistic insights

Journal of the American Chemical Society
Pankaj KumarWonwoo Nam

Abstract

New Co(III)-nitrosyl complexes bearing N-tetramethylated cyclam (TMC) ligands, [(12-TMC)Co(III)(NO)](2+) (1) and [(13-TMC)Co(III)(NO)](2+) (2), were synthesized via [(TMC)Co(II)(CH3CN)](2+) + NO(g) reactions. Spectroscopic and structural characterization showed that these compounds bind the nitrosyl moiety in a bent end-on fashion. Complexes 1 and 2 reacted with KO2/2.2.2-cryptand to produce [(12-TMC)Co(II)(NO2)](+) (3) and [(13-TMC)Co(II)(NO2)](+) (4), respectively; these possess O,O'-chelated nitrito ligands. Mechanistic studies using (18)O-labeled superoxide ((18)O2(•-)) showed that one O atom in the nitrito ligand is derived from superoxide and the O2 produced comes from the other superoxide O atom. Evidence supporting the formation of a Co-peroxynitrite intermediate is also presented.

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Citations

Feb 16, 2016·Chemical Reviews·Maan HayyanInas M AlNashef
Aug 27, 2016·Journal of the American Chemical Society·Melody R WalterTodd C Harrop
May 4, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Debabrata MukherjeeJun Okuda
Jul 28, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Kiyoshi FujisawaNicolai Lehnert
Jun 17, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Hemanta DekaBiplab Mondal
Sep 10, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Mohammed Ajmal Puthiyaveetil YoosafPankaj Kumar

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