Copper(I) Complex Mediated Nitric Oxide Reductive Coupling: Ligand Hydrogen Bonding Derived Proton Transfer Promotes N<sub>2</sub>O<sub>(g)</sub> Release

Wijeratne, Gayan B.; Bhadra, Mayukh; Siegler, Maxime A.; Karlin, Kenneth D.

doi:10.1021/jacs.9b07286

Cited by 23 publications

(24 citation statements)

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“…Mutation of a Tyr to a Phe residue in the active site of FDPnor resulted in the loss of catalytic activity, and DFT calculations implicated the Tyr as providing a key hydrogen bond to an N−N coupled hyponitrite (ONNO 2− ) intermediate during NO reduction [27c, 33] . Hydrogen bonding between the solvent and NO‐derived intermediates has also been implicated as an important factor in other synthetic complexes [7g,n] …”

Section: Resultsmentioning

confidence: 99%

A Nonheme Mononuclear {FeNO}⁷ Complex that Produces N₂O in the Absence of an Exogenous Reductant

et al. 2021

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A new nonheme iron(II) complex, FeII(Me3TACN)((OSiPh2)2O) (1), is reported. Reaction of 1 with NO(g) gives a stable mononitrosyl complex Fe(NO)(Me3TACN)((OSiPh2)2O) (2), which was characterized by Mössbauer (δ=0.52 mm s−1, |ΔEQ|=0.80 mm s−1), EPR (S=3/2), resonance Raman (RR) and Fe K‐edge X‐ray absorption spectroscopies. The data show that 2 is an {FeNO}7 complex with an S=3/2 spin ground state. The RR spectrum (λexc=458 nm) of 2 combined with isotopic labeling (15N, 18O) reveals ν(N‐O)=1680 cm−1, which is highly activated, and is a nearly identical match to that seen for the reactive mononitrosyl intermediate in the nonheme iron enzyme FDPnor (ν(NO)=1681 cm−1). Complex 2 reacts rapidly with H2O in THF to produce the N‐N coupled product N2O, providing the first example of a mononuclear nonheme iron complex that is capable of converting NO to N2O in the absence of an exogenous reductant.

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Section: Resultsmentioning

confidence: 99%

A Nonheme Mononuclear {FeNO}⁷ Complex that Produces N₂O in the Absence of an Exogenous Reductant

et al. 2021

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“…In a follow-up study, Karlin and coworkers later reported a variation of this chemistry, where a TMPA derivative was used that carries hydrogen-bond donating amide groups in the SCS . Reaction of the corresponding Cu I complex [Cu(PV-TMPA)] + (PV = pivolato) with NO was hypothesized to form a short-lived hyponitrite-bridged di-Cu II intermediate at low temperature, as determined by UV–vis spectroscopy.…”

Section: Non-heme Iron Centers and Nomentioning

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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“…Thus, hydrogen bonding likely plays an important role in facilitating NO disproportionation, much like with other examples of nearby Lewis acids and hydrogen bond donors aiding in transition metal complex reactivity with NO. [59][60][61] In particular, the hydrogen bond may help to further polarize the NO adduct, promoting its reaction with additional equivalents of nitric oxide to form a putative Co(N2O2) species. We postulate that the cobalt centers are then close enough across the pore…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

Influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks

2021

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Copper(I) Complex Mediated Nitric Oxide Reductive Coupling: Ligand Hydrogen Bonding Derived Proton Transfer Promotes N₂O_(g) Release

Cited by 23 publications

References 77 publications

A Nonheme Mononuclear {FeNO}⁷ Complex that Produces N₂O in the Absence of an Exogenous Reductant

A Nonheme Mononuclear {FeNO}⁷ Complex that Produces N₂O in the Absence of an Exogenous Reductant

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

Influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks

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Copper(I) Complex Mediated Nitric Oxide Reductive Coupling: Ligand Hydrogen Bonding Derived Proton Transfer Promotes N2O(g) Release

Cited by 23 publications

References 77 publications

A Nonheme Mononuclear {FeNO}7 Complex that Produces N2O in the Absence of an Exogenous Reductant

A Nonheme Mononuclear {FeNO}7 Complex that Produces N2O in the Absence of an Exogenous Reductant

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

Influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks

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Copper(I) Complex Mediated Nitric Oxide Reductive Coupling: Ligand Hydrogen Bonding Derived Proton Transfer Promotes N₂O_(g) Release

A Nonheme Mononuclear {FeNO}⁷ Complex that Produces N₂O in the Absence of an Exogenous Reductant

A Nonheme Mononuclear {FeNO}⁷ Complex that Produces N₂O in the Absence of an Exogenous Reductant