Dinitrosyl iron complexes (DNICs), known to form in vivo, are recognized as NO storage and delivery agents. As such, a library of biomimetic DNICs has been synthesized and studied. Although much is known about the chemistry and biochemistry of these biomimetic complexes, including their role as NO release agents, the features that control NO release/transfer remain elusive. Of the few studies that have explored NO release/transfer, none have considered metal-promoted NO release. As copper is known to facilitate the breakdown of S-nitrosothiols (RSNOs), which, along with DNICs, act as NO storage and delivery agents, we explore a potential role for copper in the release of NO from DNICs. We synthesized and structurally characterized a neocuproine (neo)-bound DNIC, which was then treated with either CuI or CuII salts. The reactions with CuX, where X = Cl, Br, or PF6, proceed via a simple ligand exchange reaction, producing NO and the well-studied copper complex [Cu(neo)2]X. Addition of the CuII salts also produce NO, but in this case, a redox reaction occurs in which the Cu is reduced and the Fe(NO)2 unit is oxidized. Full characterization of the products and determination of the rates of these reactions are ongoing.

Interplay of copper and iron in NO release from Dinitrosyl Iron Complexes (DNICs)

253rd National Meeting (2017)

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