Insight into the Electronic Structure of Biomimetic Dinitrosyliron Complexes (DNICs): Toward the Syntheses of Amido-Bridging Dinuclear DNICs

Abstract

The ubiquitous function of nitric oxide (NO) guided the biological discovery of the natural dinitrosyliron unit (DNIU) [Fe(NO)₂] as an intermediate/end product after Fe nitrosylation of nonheme cofactors. Because of the natural utilization of this cofactor for the biological storage and delivery of NO, a bioinorganic study of synthetic dinitrosyliron complexes (DNICs) has been extensively explored in the last 2 decades. The bioinorganic study of DNICs involved the development of synthetic methodology, spectroscopic discrimination, biological application of NO-delivery reactivity, and translational application to the (catalytic) transformation of small molecules. In this Forum Article, we aim to provide a systematic review of spectroscopic and computational insights into the bonding nature within the DNIU [Fe(NO)₂] and the electronic structure of different types of DNICs, which highlights the synchronized advance in synthetic methodology and spectroscopic tools. With regard to the noninnocent nature of a NO ligand, spectroscopic and computational tools were utilized to provide qualitative/quantitative assignment of oxidation states of Fe and NO in DNICs with different redox levels and ligation modes as well as to probe the Fe-NO bonding interaction modulated by supporting ligands. Besides the strong antiferromagnetic coupling between high-spin Fe and paramagnetic NO ligands within the covalent DNIU [Fe(NO)₂], in polynuclear DNICs, the effects of the Fe···Fe distance, nature of the bridging ligands, and type of bridging modes on the regulation of the magnetic coupling among paramagnetic DNIU [Fe(NO)₂] are further reviewed. In the last part of this Forum Article, the sequential reaction of {Fe(NO)₂}¹⁰ DNIC [(NO)₂Fe(AMP)] (1-red) with NO_(g), HBF₄, and KC₈ establishes a synthetic cycle, {Fe(NO)₂}⁹-{Fe(NO)₂}⁹ DNIC [(NO)₂Fe(μ-dAMP)₂Fe(NO)₂] (1) → {Fe(NO)₂}⁹ DNIC [(NO₂)Fe(AMP)][BF₄] (1-H) → {Fe(NO)₂}¹⁰ DNIC 1-red → DNIC 1, for the transformation of NO into HNO/N₂O. Of importance, the NO-induced transformation of {Fe(NO)₂}¹⁰ DNIC 1-red and [(NO)₂Fe(DTA)] (2-red; DTA = diethylenetriamine) unravels a synthetic strategy for preparation of the {Fe(NO)₂}⁹-{Fe(NO)₂}⁹ DNICs [(NO)₂Fe(μ-NHR)₂Fe(NO)₂] containing amido-bridging ligands, which hold the potential to feature distinctive physical properties, chemical reactivities, and biological applications.