Acetate-induced demetalation of a {gamma-SiW(10)Fe(2)}-based dimer affords an acetato/hydroxo-bridged triiron cluster stabilized by two isomerically distinct Keggin units.
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http://dx.doi.org/10.1039/b905211a | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry, University of California Berkeley, Berkeley, California 94720, United States.
In Nature, the four-electron reduction of O is catalyzed at preorganized multimetallic active sites. These complex active sites often feature low-coordinate, redox-active metal centers precisely positioned to facilitate rapid O activation processes that obviate the generation of toxic, partially reduced oxygen species. Very few biomimetic constructs simultaneously recapitulate the complexity and reactivity of these biological cofactors.
View Article and Find Full Text PDFMolecules
July 2024
Laboratoire de Chimie, Electrochimie Moléculaire et Chimie Analytique, UMR 6521 CNRS-Université de Bretagne Occidentale, CS 93837-6 Avenue Le Gorgeu, CEDEX 3, 29238 Brest, France.
Acta Crystallogr E Crystallogr Commun
May 2024
Nanjing Normal University, 1 Wenyuan Road, Qixia district, Nanjing, Jiangsu 210023, People's Republic of China.
The title compound, tetra-ethyl-ammonium tri-azido-tri-μ-sulfido-[μ-(tri-methyl-sil-yl)aza-nediido][tris-(3,5-di-methyl-pyrazol-1-yl)hydro-borato]triiron(+2.33)molybdenum(IV), (CHN)[FeMoS(CHBN)(CHNSi)(N)] or (EtN)[(Tp*)MoFeS(μ-NSiMe)(N)] [Tp* = tris-(3,5-di-methyl-pyrazol-1-yl)hydro-bor-ate(1-)], crystallizes as needle-like black crystals in space group . In this cluster, the Mo site is in a distorted octa-hedral coordination model, coordinating three N atoms on the Tp* ligand and three μ-bridging S atoms in the core.
View Article and Find Full Text PDFJ Phys Chem C Nanomater Interfaces
December 2023
Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Avenue S.E., Minneapolis, Minnesota 55455, United States.
High-valent Fe(IV)-oxo species derived upon reactions of NO with Fe(II) centers-embedded in the framework of tri-iron oxo-centered-based metal-organic frameworks (MOFs)- selectively affect the conversion of benzene-to-phenol via electrophilic addition to arene C-H bonds akin to oxygen transfer mechanisms in the P450 enzyme. The Fe(II) species identified by Mössbauer spectroscopy can be titrated in situ by the addition of NO to completely suppress benzene oxidation, verifying the relevance of Fe(II) centers. Observed inverse kinetic isotope effects in benzene hydroxylation preclude the involvement of H atom transfer steps from benzene to the Fe(IV)-oxo species and instead suggest that the electrophilic iron-oxo group adds to an sp carbon of benzene, resulting in a change in the hybridization from sp-to-sp.
View Article and Find Full Text PDFCell Res
March 2022
Division of Respiratory and Critical Care Medicine, Respiratory Infection and Intervention Laboratory of Frontiers Science Center for Disease-related Molecular Network, State Key Laboratory of Biotherapy, West China Hospital of Sichuan University, Chengdu, Sichuan, China.
Methanobactins (Mbns) are a family of copper-binding peptides involved in copper uptake by methanotrophs, and are potential therapeutic agents for treating diseases characterized by disordered copper accumulation. Mbns are produced via modification of MbnA precursor peptides at cysteine residues catalyzed by the core biosynthetic machinery containing MbnB, an iron-dependent enzyme, and MbnC. However, mechanistic details underlying the catalysis of the MbnBC holoenzyme remain unclear.
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