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A Mononuclear Nonheme Iron(IV)–Amido Complex Relevant for the Compound II Chemistry of Cytochrome P450

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.8b11045· OSTI ID:1493335

A mononuclear nonheme iron(IV)–amido complex bearing a tetraamido macrocyclic ligand, [(TAML)FeIV(NHTs)]- (1), was synthesized via a hydrogen atom (H atom) abstraction reaction of an iron(V)–imido complex, [(TAML)FeV(NTs)]- (2), and fully characterized using various spectroscopies. We then investigated (1) the pKa of 1, (2) the reaction of 1 with a carbon-centered radical, and (3) the H atom abstraction reaction of 1. To the best of our knowledge, the present study reports for the first time the synthesis and chemical properties/reactions of a high-valent iron(IV)–amido complex.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Institutes of Health (NIH)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1493335
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 1 Vol. 141; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (42)

Oxidation Reactions with Bioinspired Mononuclear Non-Heme Metal-Oxo Complexes journal June 2016
Elimination Mechanisms in the Aminolysis of Sulfamate Esters of the Type NH 2 SO 2 OC 6 H 4 X - Models of Enzyme Inhibitors journal August 2008
Preparation of Compound I in P450 cam : The Prototypical P450 journal July 2016
Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation journal December 2016
A new look at the role of thiolate ligation in cytochrome P450 journal January 2017
Dioxygen activation by nonheme iron enzymes with the 2-His-1-carboxylate facial triad that generate high-valent oxoiron oxidants journal January 2017
C-H bond amination by iron-imido/nitrene species journal April 2012
Nitrido and imido transition metal complexes of Groups 6–8 journal August 2003
C-H bond activation in heme proteins: the role of thiolate ligation in cytochrome P450 journal February 2009
ME and ME complexes of iron and cobalt that emphasize three-fold symmetry (E=O, N, NR) journal April 2011
X-ray absorption near-edge spectroscopy in bioinorganic chemistry: Application to M–O2 systems journal January 2013
Acid-catalyzed disproportionation of oxoiron(IV) porphyrins to give oxoiron(IV) porphyrin radical cations journal June 2011
Molecular Designs for Controlling the Local Environments around Metal Ions journal July 2015
Toward the Synthesis of More Reactive S = 2 Non-Heme Oxoiron(IV) Complexes journal July 2015
Hydrogen Atom Transfer Reactions of Mononuclear Nonheme Metal–Oxygen Intermediates journal August 2018
O 2 Activation by Non-Heme Iron Enzymes journal November 2016
Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins journal December 2017
Tuning Reactivity and Mechanism in Oxidation Reactions by Mononuclear Nonheme Iron(IV)-Oxo Complexes journal February 2014
Hydrogen Atom Abstraction by Metal−Oxo Complexes:  Understanding the Analogy with Organic Radical Reactions journal August 1998
Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications journal December 2010
P450 Enzymes: Their Structure, Reactivity, and Selectivity—Modeled by QM/MM Calculations journal February 2010
Hydrocarbon Hydroxylation by Cytochrome P450 Enzymes journal February 2010
Kinetics and Mechanism of Oxidation Reactions of Porphyrin−Iron(IV)−Oxo Intermediates journal August 2007
High valent transition metal chemistry. Synthesis and characterization of an intermediate-spin iron(IV) complex of a strong .pi.-acid ligand journal October 1992
Thermodynamics of Hydrogen Atom Transfer to a High-Valent Iron Imido Complex journal March 2008
Copper(II) Anilides in sp 3 C-H Amination journal July 2014
A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes journal July 1997
Characterization of Iron-Imido Species Relevant for N -Group Transfer Chemistry journal February 2016
Spectroscopic Investigations of Catalase Compound II: Characterization of an Iron(IV) Hydroxide Intermediate in a Non-thiolate-Ligated Heme Enzyme journal November 2016
A Mononuclear Nonheme Iron(V)-Imido Complex journal June 2017
Direct Observation of Oxygen Rebound with an Iron-Hydroxide Complex journal September 2017
Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex journal October 2017
Observation of Radical Rebound in a Mononuclear Nonheme Iron Model Complex journal February 2018
The triphenylmethyl radical: equilibrium measurements and the reaction with thiophenol journal June 1978
Significantly shorter Fe–S bond in cytochrome P450-I is consistent with greater reactivity relative to chloroperoxidase journal August 2015
Characterization of a selenocysteine-ligated P450 compound I reveals direct link between electron donation and reactivity journal May 2017
To rebound or dissociate? This is the mechanistic question in C–H hydroxylation by heme and nonheme metal–oxo complexes journal January 2016
Selective functionalisation of saturated C–H bonds with metalloporphyrin catalysts journal January 2011
Heme-thiolate ferryl of aromatic peroxygenase is basic and reactive journal March 2015
Terminal Nitrido and Imido Complexes of the late Transition Metals journal March 2009
Oxoiron(IV) in Chloroperoxidase Compound II Is Basic: Implications for P450 Chemistry journal June 2004
Iron(IV)hydroxide pKa and the Role of Thiolate Ligation in C-H Bond Activation by Cytochrome P450 journal November 2013

Cited By (2)

Octahedral iron( iv )–tosylimido complexes exhibiting single electron-oxidation reactivity journal January 2019
A designed second-sphere hydrogen-bond interaction that critically influences the O–O bond activation for heterolytic cleavage in ferric iron–porphyrin complexes journal January 2020

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