TY - JOUR
T1 - Reactivity of high-valent iron-oxo species in enzymes and synthetic reagents
T2 - A tale of many states
AU - Shaik, Sason
AU - Hirao, Hajime
AU - Kumar, Devesh
PY - 2007/7
Y1 - 2007/7
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=34547725316&partnerID=8YFLogxK
U2 - 10.1021/ar600042c
DO - 10.1021/ar600042c
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C2 - 17488054
AN - SCOPUS:34547725316
SN - 0001-4842
VL - 40
SP - 532
EP - 542
JO - Accounts of Chemical Research
JF - Accounts of Chemical Research
IS - 7
ER -