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Formation and High Reactivity of the anti ‐Dioxo Form of High‐Spin μ‐Oxodioxodiiron(IV) as the Active Species That Cleaves Strong C−H Bonds
Author(s) -
Kodera Masahito,
Ishiga Shin,
Tsuji Tomokazu,
Sakurai Katsutoshi,
Hitomi Yutaka,
Shiota Yoshihito,
Sajith P. K.,
Yoshizawa Kazunari,
Mieda Kaoru,
Ogura Takashi
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600048
Subject(s) - ethylbenzene , chemistry , reactivity (psychology) , cumene , toluene , substrate (aquarium) , reaction rate constant , catalysis , photochemistry , bond cleavage , medicinal chemistry , double bond , catalytic cycle , kinetic isotope effect , kinetics , organic chemistry , medicine , oceanography , alternative medicine , physics , pathology , quantum mechanics , deuterium , geology
Recently, it was shown that μ‐oxo‐μ‐peroxodiiron(III) is converted to high‐spin μ‐oxodioxodiiron(IV) through O−O bond scission. Herein, the formation and high reactivity of the anti ‐dioxo form of high‐spin μ‐oxodioxodiiron(IV) as the active oxidant are demonstrated on the basis of resonance Raman and electronic‐absorption spectral changes, detailed kinetic studies, DFT calculations, activation parameters, kinetic isotope effects (KIE), and catalytic oxidation of alkanes. Decay of μ‐oxodioxodiiron(IV) was greatly accelerated on addition of substrate. The reactivity order of substrates is toluene