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N-N Coupling of Nitrosyl Ligands in a Dinitrosyl Iron Complex Mediated by Exogenous Acids
Ethan Zars1, Daniel M Beagan1, Sarah R Reed1
1Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, United States.
Abstract:
We disclose the synthesis, characterization, and reactivity profiles of a dinitrosyl iron complex (DNIC) toward exogenous Brønsted and Lewis acids. Treatment of the {Fe(NO)2}10 complex (butylNN)Fe(NO)2 (1) (butylNN = 2-(1-butyl-5(tert-butyl)-1H-pyrazol-3-yl)-6-methylpyridine) with a variety of Brønsted and Lewis acids generates an oxidized {Fe(NO)2}9 species [(butylNN)Fe(NO)2][PF6] (2-PF6) and, in the presence of a radical reagent, N2O. The pathway for N2O formation is governed by acid additives, and mechanistic studies indicate that the acid promotes electron transfer from the iron center in 1 and facilitates NO lability, providing a pathway for N2O formation.
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