Lewis Acid Coordination Redirects S‐Nitrosothiol Signaling Output

Hosseininasab, Valiallah; McQuilken, Alison C.; Bakhoda, Abolghasem; Bertke, Jeffery A.; Timerghazin, Qadir K.; Warren, Timothy H.

doi:10.1002/anie.202001450

Cited by 20 publications

(11 citation statements)

References 43 publications

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“…It is well-known that coordination of RSNO to metal center or Lewis acid via S, O, N atoms can alter the strength of N=O and S-N bond. [23,[37][38][39][40] While k 1 -N coordination of S-nitrosothiols weakens the N=O bond and strengthens the N-S bond, k 1 -S coordination has the opposite effects (Scheme 5A). Therefore, the higher N=O stretches of dicopper(I,I)-bound PE-SNO (1512 and 1505 cm -1 ) in comparison to free PE-SNO (1495 cm -1 , Figure S64-65) strongly suggests that the S atoms of PE-SNO also coordinate/interact with the Cu(I) center.…”

Section: Characterization Of [Lcu I 2(pe-sno)2] 2+ Adduct 3-pementioning

confidence: 99%

Redox‐Neutral S‐nitrosation Mediated by a Dicopper Center

2021

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An unprecedented redox-neutral S-nitrosation of thiol has been achieved at dicopper(I,I) center. Treatment of dicopper (I,I) complex with excess NO • and thiol generates a dicopper (I,I) di-Snitrosothiol complex [Cu I Cu I (RSNO)2] 2+ or dicopper (I,I) mono-Snitrosothiol complex [Cu I Cu I (RSNO)] 2+ , which readily release RSNO in 88-94% yield. The S-nitrosation reaction proceeds through a mixedvalence [Cu II Cu III (-O)(-NO)] 2+ species, which deprotonates RS-H at the basic -O site and nitrosates the RS − at the -NO site. The [Cu II Cu III (-O)(-NO)] 2+ complex is also competent for O-nitrosation of MeOH, which is isoelectronic to thiol. In this case, a rare [Cu II Cu II (-NO)(OMe)] 2+ intermediate has been isolated and fully characterized, suggesting the S-nitrosation proceeds through the intermediary of analogous [Cu II Cu II (-NO)(SR)] 2+ species. The redox-and protonneutral S-nitrosation process reported here represents the first functional model of ceruloplasmin in mediating S-nitrosation of external thiols, adding further implications for biological copper sites in the interconversion of NO • /RSNO.

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Section: Characterization Of [Lcu I 2(pe-sno)2] 2+ Adduct 3-pementioning

confidence: 99%

Redox‐Neutral S‐nitrosation Mediated by a Dicopper Center

2021

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“…In biomimetic model studies, transition-metal-complex-mediated NO conversion to N 2 O via inter/intramolecular ON–NO coupling has been explored (Scheme A). − The reductive conversion of ·NO to N 2 O via the formation of hyponitrite-bound intermediate ([ON] − –[NO] − coupling promoted by ligating two Fe-/Ru-nitrosyl moieties, , stabilized by Lewis acid or hydrogen-bonding interactions , ) was demonstrated. In particular, it has been reported that the highly reduced [NO] 2– -bound complexes possessing a stronger nucleophilicity promote ·NO electrophilic attack to form hyponitrite-bound complexes (Scheme B). − NO disproportionation yielding nitrite and N 2 O triggered by transition-metal (Fe, Cu, Ni, Co, Ru, and Mn) complexes was also proposed (Scheme C). − Despite several literature reports on the transition-metal-mediated reduction of NO to N 2 O, the detailed conversion pathways of NO to N 2 O via competition between the generation of the [N 2 O 2 ] 2– -bound intermediate and the formation of the [N 2 O 2 ] ·– -bound intermediate originated from metal-mediated NO disproportionation remain elusive.…”

Section: Introductionmentioning

confidence: 99%

NO Reduction to N₂O Triggered by a Dinuclear Dinitrosyl Iron Complex via the Associated Pathways of Hyponitrite Formation and NO Disproportionation

Tsai

Lai

et al. 2021

Inorg. Chem.

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In spite of the comprehensive study of the metal-mediated conversion of NO to N 2 O disclosing the conceivable processes/mechanism in biological and biomimetic studies, in this study, the synthesis cycles and mechanism of NO reduction to N 2 O triggered by the electronically localized dinuclear {Fe(NO) 2 } 10 −{Fe(NO) 2 } 9 dinitrosyl iron complex (DNIC) [Fe(NO) 2 (μbdmap)Fe(NO) 2 (THF)] (1) (bdmap = 1,3-bis(dimethylamino)-2-propanolate) were investigated in detail. Reductive conversion of NO to N 2 O triggered by complex 1 in the presence of exogenous •NO occurs via the simultaneous formation of hyponitritebound {[Fe 2 (NO) 4 (μ-bdmap)] 2 (κ 4 -N 2 O 2 )} (2) and [NO 2 ] − -bridged [Fe 2 (NO) 4 (μ-bdmap)(μ-NO 2 )] (3) (NO disproportionation yielding N 2 O and complex 3). EPR/IR spectra, single-crystal X-ray diffraction, and the electrochemical study uncover the reversible redox transformation of {Fe(NO) 2 } 9 -{Fe(NO) 2 } 9 [Fe 2 (NO) 4 (μ-bdmap)(μ-OC 4 H 8 )] + (7) ↔ {Fe(NO) 2 } 10 -{Fe(NO) 2 } 9 1 ↔ {Fe(NO) 2 } 10 -{Fe(NO) 2 } 10 [Fe(NO) 2 (μ-bdmap)Fe(NO) 2 ] − (6) and characterize the formation of complex 1. Also, the synthesis study and DFT computation feature the detailed mechanism of electronically localized {Fe(NO) 2 } 10 −{Fe(NO) 2 } 9 DNIC 1 reducing NO to N 2 O via the associated hyponitrite-formation and NO-disproportionation pathways. Presumably, the THF-bound {Fe(NO) 2 } 9 unit of electronically localized {Fe(NO) 2 } 10 -{Fe(NO) 2 } 9 complex 1 served as an electron buffering reservoir for accommodating electron redistribution, and the {Fe(NO) 2 } 10 unit of complex 1 acted as an electron-transfer channel to drive exogeneous •NO coordination to yield proposed relay intermediate κ 2 -N,O-[NO] − -bridged [Fe 2 (NO) 4 (μ-bdmap)(μ-NO)] (A) for NO reduction to N 2 O.

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“…These cooperative interactions are proposed to bias substrate coordination, stabilize high-energy transition states, and facilitate charge transfer . By emulating these properties in synthetic systems, transition-metal/Lewis acid (LA) systems have achieved improvements in reactivity and selectivity for organic reactions, , lowered overpotentials for electrocatalysis, , enabled small molecule activation, , and accelerated cross-coupling reactions . Because the mode of activation is substrate-dependent among these systems, the observed improvements to reactivity necessarily proceed through distinct mechanisms.…”

Section: Introductionmentioning

confidence: 99%

Lewis Acid Effects on Calculated Ligand Electronic Parameters

Shanahan

Szymczak

2020

Organometallics

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Adding Lewis acids to coordinated ligands can impart systematic changes to their properties. We computationally explored the effects of acid-induced changes to the donor strength (Tolman electronic parameter) of 17 ligands, in addition to changes to the charge distribution and binding energies for a representative set of ligands. These results were compared using a combined experimental/computational study with cyanide. The combined results demonstrate: (1) large effects for the initial binding of even weak Lewis acids, with smaller changes as Lewis acidity is increased, (2) Lewis acid modifications afford smaller tunability than covalent substitution (Hammett parameters), and (3) binding energy provides a reasonable guide that can be used for designing cooperative interactions.

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Lewis Acid Coordination Redirects S‐Nitrosothiol Signaling Output

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 20 publications

References 43 publications

Redox‐Neutral S‐nitrosation Mediated by a Dicopper Center

Redox‐Neutral S‐nitrosation Mediated by a Dicopper Center

NO Reduction to N₂O Triggered by a Dinuclear Dinitrosyl Iron Complex via the Associated Pathways of Hyponitrite Formation and NO Disproportionation

Lewis Acid Effects on Calculated Ligand Electronic Parameters

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Lewis Acid Coordination Redirects S‐Nitrosothiol Signaling Output

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 20 publications

References 43 publications

Redox‐Neutral S‐nitrosation Mediated by a Dicopper Center

Redox‐Neutral S‐nitrosation Mediated by a Dicopper Center

NO Reduction to N2O Triggered by a Dinuclear Dinitrosyl Iron Complex via the Associated Pathways of Hyponitrite Formation and NO Disproportionation

Lewis Acid Effects on Calculated Ligand Electronic Parameters

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NO Reduction to N₂O Triggered by a Dinuclear Dinitrosyl Iron Complex via the Associated Pathways of Hyponitrite Formation and NO Disproportionation