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Experiment and Theory Reveal the Fundamental Difference between Two‐State and Single‐State Reactivity Patterns in Nonheme Fe IV O versus Ru IV O Oxidants
Author(s) -
Dhuri Sunder N.,
Seo Mi Sook,
Lee YongMin,
Hirao Hajime,
Wang Yong,
Nam Wonwoo,
Shaik Sason
Publication year - 2008
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.200705880
Subject(s) - reactivity (psychology) , electrophile , chemistry , abstraction , state (computer science) , ligand (biochemistry) , excited state , ground state , electron transfer , content (measure theory) , oxidation state , medicinal chemistry , computational chemistry , stereochemistry , photochemistry , epistemology , organic chemistry , philosophy , atomic physics , physics , catalysis , computer science , mathematics , medicine , alternative medicine , pathology , algorithm , mathematical analysis , biochemistry , receptor
Two‐state reactivity involving close triplet ground and quintet excited states is responsible for the opposite reactivity trends of Fe IV oxo complexes in O‐transfer and H‐abstraction reactions in dependence on the electron richness of the axial ligand X (see picture), as shown by comparison with Ru IV analogues, in which both reactivities are solely governed by the electrophilicity of the complex because the quintet state is inaccessible.