Electronic Structure and Transformation of Dinitrosyl Iron Complexes (DNICs) Regulated by Redox Non-Innocent Imino-Substituted Phenoxide Ligand.

ABSTRACT: The coupled NO-vibrational peaks [IR ν_NO 1775 s, 1716 vs, 1668 vs cm^-1 (THF)] between two adjacent [Fe(NO)₂] groups implicate the electron delocalization nature of the singly O-phenoxide-bridged dinuclear dinitrosyliron complex (DNIC) [Fe(NO)₂(μ-ON₂^Me)Fe(NO)₂] (1). Electronic interplay between [Fe(NO)₂] units and [ON₂^Me]^- ligand in DNIC 1 rationalizes that "hard" O-phenoxide moiety polarizes iron center(s) of [Fe(NO)₂] unit(s) to enforce a "constrained" π-conjugation system acting as an electron reservoir to bestow the spin-frustrated {Fe(NO)₂}⁹-{Fe(NO)₂}⁹-[^·ON₂^M

SUBMITTER: Wu WY 

PROVIDER: S-EPMC10848267 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature