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Two Faces of a Biomimetic Non‐Heme HOFe V O Oxidant: Olefin Epoxidation versus cis ‐Dihydroxylation
Author(s) -
Bassan Arianna,
Blomberg Margareta R. A.,
Siegbahn Per E. M.,
Que Lawrence
Publication year - 2005
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200463072
Subject(s) - dihydroxylation , olefin fiber , chemistry , reactivity (psychology) , ligand (biochemistry) , epoxide , amine gas treating , density functional theory , medicinal chemistry , catalysis , stereochemistry , diol , heme , computational chemistry , organic chemistry , enantioselective synthesis , medicine , biochemistry , alternative medicine , receptor , pathology , enzyme
Reactivity along two channels is shown by the HOFe V O species responsible for Fe(tpa)‐catalyzed olefin oxidation (tpa=tris(2‐pyridylmethyl)amine). Attack of the oxo ligand on an olefinic carbon atom yields epoxide and attack of the hydroxo ligand affords cis ‐diol (see scheme). Hybrid density functional theory now demonstrates that the two processes have comparable activation energies.