A Nonheme Sulfur‐Ligated {FeNO}⁶ Complex and Comparison with Redox‐Interconvertible {FeNO}⁷ and {FeNO}⁸ Analogues

Abstract

A nonheme {FeNO} complex, [Fe(NO)(N3PyS)] , was synthesized by reversible, one-electron oxidation of an {FeNO} analogue. This complex completes the first known series of sulfur-ligated {FeNO} complexes. All three {FeNO} complexes are readily interconverted by one-electron oxidation/reduction. A comparison of spectroscopic data (UV/Vis, NMR, IR, Mössbauer, X-ray absorption) provides a complete picture of the electronic and structural changes that occur upon {FeNO} -{FeNO} interconversion. Dissociation of NO from the new {FeNO} complex is shown to be controlled by solvent, temperature, and photolysis, which is rare for a sulfur-ligated {FeNO} species.

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

“…We speculated that a mononuclear nonheme iron center, with an appropriate ligand environment, might have the minimal attributes needed to activate NO toward N−N bond formation and N−O cleavage to give N 2 O, circumventing the need for a dinuclear system by taking advantage of the diffusional reactivity accessible to small molecules. Our initial efforts led to a sulfur‐ligated mononuclear iron complex ([Fe II (N3PyS)] + ) that supported the binding of NO in a rare series of redox‐interconvertible {FeNO} 6–8 species with identical ligand environments [12] . Reversible one‐electron reduction of the {FeNO} 7 complex gave an {FeNO} 8 complex, which then decayed to produce N 2 O in sub‐stoichiometric yield (54 %) [13] .…”

Stepwise nitrosylation of the nonheme iron site in an engineered azurin and a molecular basis for nitric oxide signaling mediated by nonheme iron proteins

“…22 Pioneered by Wieghardt et al reporting the first comprehensive characterization of the lowspin {FeNO} [6][7][8] complexes, 23 a series of {FeNO} [6][7][8] and highly reduced {FeNO} [8][9][10] complexes have been spectroscopically and structurally characterized. [24][25][26][27] Lehnert group reported the first series of high-spin {FeNO} [6][7][8] complexes and demonstrated that the redox transformation of high-spin {FeNO} [6][7][8] were all ironbased contrasted to corresponding low-spin complexes where redox transformation was generally NO centered. 28 Most recently, Meyer and coworkers synthesized an complete series of five {FeNO} [6][7][8][9][10] complexes with one ligand scaffold.…”

Preise der American Chemical Society 2020

“…Lancasters Gruppe untersucht Beziehungen zwischen elektronischer Struktur und Funktion bei Katalysen mit unedlen Metallen in Synthese und Biologie mit Schwerpunkten auf C‐H‐Funktionalisierung und Ammoniakoxidation. In einer Zuschrift in der Angewandten Chemie verglich er verschiedene Eisen‐Nitroso‐Komplexe mit Schwefelliganden …”