Reactivity of high-valent iron-oxo species in enzymes and synthetic reagents: A tale of many states

Sason Shaik*, Hajime Hirao, Devesh Kumar

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

485 Scopus citations

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.

Original languageEnglish
Pages (from-to)532-542
Number of pages11
JournalAccounts of Chemical Research
Volume40
Issue number7
DOIs
StatePublished - Jul 2007

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