Structural and Electronic Responses to the Three Redox Levels of Fe(NO)N2S2‐Fe(NO)2

Ghosh, Pijush K.; Ding, Shengda; Quiroz, Manuel; Bhuvanesh, Nattamai; Hsieh, Chieh; Palacios, Philip M.; Pierce, Brad S.; Darensbourg, Marcetta Y.; Hall, Michael B.

doi:10.1002/chem.201804168

Cited by 13 publications

(17 citation statements)

References 38 publications

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“…Spectroscopic discriminations of these different types of DNICs by EPR spectroscopy, infrared (IR) spectroscopy, Fe/S K-edge X-ray absorption near-edge spectroscopy, and 15 N NMR were reviewed elsewhere . In the following sessions, we will review the spectroscopic and computational insights into the bonding nature within the [Fe(NO) 2 ] unit and the electronic structure of classical DNICs, whereas the study of metallothiolate-bound DNICs is reported in other literature. − …”

Section: Results and Discussion: Bonding Nature And Electronic Struct...mentioning

confidence: 99%

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

Tung

Tseng

et al. 2021

Inorg. Chem.

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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) 2 Fe(AMP)] (1-red) with NO (g) , HBF 4 , and KC 8 establishes a synthetic cycle, {Fe(NO) 2 } 9 -{Fe(NO) 2 } 9 DNIC [(NO) 2 Fe(μ-dAMP) 2 Fe(NO) 2 ] (1) → {Fe(NO) 2 } 9 DNIC [(NO 2 )Fe(AMP)][BF 4 ] (1-H) → {Fe(NO) 2 } 10 DNIC 1-red → DNIC 1, for the transformation of NO into HNO/N 2 O. Of importance, the NO-induced transformation of {Fe(NO) 2 } 10 DNIC 1-red and [(NO) 2 Fe(DTA)] (2-red; DTA = diethylenetriamine) unravels a synthetic strategy for preparation of the {Fe(NO) 2 } 9 -{Fe(NO) 2 } 9 DNICs [(NO) 2 Fe(μ-NHR) 2 Fe(NO) 2 ] containing amido-bridging ligands, which hold the potential to feature distinctive physical properties, chemical reactivities, and biological applications.

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Section: Results and Discussion: Bonding Nature And Electronic Struct...mentioning

confidence: 99%

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

Tung

Tseng

et al. 2021

Inorg. Chem.

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“… Darensbourg and coworkers developed the butterfly M(μ-SR) 2 M’ type diiron complex 248 that mimics the [FeFe] hydrogenase active site with an AF coupled {FeNO} 7 -{Fe(NO) 2 } 9 center, which reacts with strong acid leading to H 2 evolution . The key to success of this catalyst appears to be the coopertivity of the two iron nitrosyl units, both of which can accommodate redox changes, resulting in efficient electron transfer, storage, and proton reduction. , This particular system opened up an avenue for future exploration of different carbon backbones and different metal active sites for HER catalysts including complex 264 . , …”

Section: Dinitrosyl Iron Complexes (Dnics)mentioning

confidence: 99%

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

et al. 2021

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Nitric oxide (NO) is an important signaling molecule that is involved in a wide range of physiological and pathological events in biology. Metal coordination chemistry, especially with iron, is at the heart of many biological transformations involving NO. A series of heme proteins, nitric oxide synthases (NOS), soluble guanylate cyclase (sGC), and nitrophorins, are responsible for the biosynthesis, sensing, and transport of NO. Alternatively, NO can be generated from nitrite by heme- and copper-containing nitrite reductases (NIRs). The NO-bearing small molecules such as nitrosothiols and dinitrosyl iron complexes (DNICs) can serve as an alternative vehicle for NO storage and transport. Once NO is formed, the rich reaction chemistry of NO leads to a wide variety of biological activities including reduction of NO by heme or non-heme iron-containing NO reductases and protein post-translational modifications by DNICs. Much of our understanding of the reactivity of metal sites in biology with NO and the mechanisms of these transformations has come from the elucidation of the geometric and electronic structures and chemical reactivity of synthetic model systems, in synergy with biochemical and biophysical studies on the relevant proteins themselves. This review focuses on recent advancements from studies on proteins and model complexes that not only have improved our understanding of the biological roles of NO but also have provided foundations for biomedical research and for bio-inspired catalyst design in energy science.

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“…NO transfer between transition metals is known to be mechanistically diverse, leading, on the chemists’ benchtop, to thermodynamically controlled, self-assembly products . Such was the case in the preparation of the diiron trinitrosyl complex A , shown in the upper left corner of Figure and accessible by myriad routes. , The right-hand corner shows the neutral W(CO) 4 derivative B , which is displayed in several neutral (N 2 S 2 )M [N 2 S 2 = N , N -bis(2-mercaptoethyl)-1,4-diazacycloheptane] metalloligands where M 2+ = Ni, VO, Fe(NO), and (shown here) Co(NO) . The CO ligands reported on the donor abilities of the metal-modified dithiolates according to ν(CO) IR values in the stable tungsten carbonyl reference compounds .…”

Section: Introductionmentioning

confidence: 99%

Linear and Bent Nitric Oxide Ligand Binding in an Asymmetric Butterfly Complex: CoMoCo′

et al. 2021

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Two synthetic approaches to install metallodithiolate ligands on molybdenum centers using the synthons [Mo 2 (CH 3 CN) 10 ] 4+ and (N 2 S 2 )Co(NO) [N 2 S 2 = N,N-bis(2-mercaptoethyl)-1,4-diazacycloheptane and NO = nitric oxide], or [Mo(NO) 2 (CH 3 CN) 4 ] 2+ (CH 3 CN = acetonitrile) and [(N 2 S 2 )Co] 2 lead to a bisnitrosylated, trimetallic dication, CoMoCo′. This unique asymmetric butterfly complex, with S = 1, has a bent NO within the small {Co(NO)} 8 wing (denoted as Co), reflecting Co III (NO − ), and is S-bridged to a linear {Mo(NO)} 6 diamagnetic unit. The latter is further S-bridged to a pentacoordinate (N 2 S 2 )Co III (CH 3 CN) donor in the larger wing and is the origin of the two unpaired electrons, denoted as Co′. The asymmetry in Mo−Co distances, 3.33 Å in the Co wing and 2.73 Å in the Co′ wing, indicated a Mo−Co′ bonding interaction. The transfer of NO from (N 2 S 2 )Co(NO) in the former path is needed to cleave the strong quadruple bond in [Mo≣Mo] 4+ , with the energetic cost compensated for via a one-electron bond between Mo and Co′, as indicated by natural bonding orbital analysis.

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Structural and Electronic Responses to the Three Redox Levels of Fe(NO)N₂S₂‐Fe(NO)₂

Cited by 13 publications

References 38 publications

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

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

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

Linear and Bent Nitric Oxide Ligand Binding in an Asymmetric Butterfly Complex: CoMoCo′

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