title: Reactivity of high-valent iron-oxo species in enzymes and synthetic reagents: a tale of many states.
abstract: The Account discusses the phenomenon of two-state reactivity (TSR) or multistate reactivity (MSR) in high-valent metal-oxo reagents, projecting its wide-ranging applicability starting from the bare species, through the reagents made by Que, Nam, and collaborators, to the Mn(V)-oxo substituted polyoxometalate, all the way to Compound I species of heme enzymes. The Account shows how the behaviors of all these variegated species derive from a simple set of electronic structure principles. Experimental trends that demonstrate TSR and MSR are discussed. Diagnostic mechanistic probes are proposed for the TSR/MSR scenario, based on kinetic isotope effect, stereochemical studies, and magnetic- and electric-field effects.
authors.affiliation: Department of Organic Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel. sason@yfaat.ch.huji.ac.il
authors.forename: Sason
authors.initials: S
authors.lastname: Shaik
authors.forename: Hajime
authors.initials: H
authors.lastname: Hirao
authors.forename: Devesh
authors.initials: D
authors.lastname: Kumar
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry; D004563:Electrochemistry; D004798:Enzymes / Q000737:chemistry*; D007202:Indicators and Reagents; D007501:Iron / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry*
chemical_list: D004798:Enzymes; D007202:Indicators and Reagents; C066318:perferryl iron; D007501:Iron; D010100:Oxygen