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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
C-H Bond Activation by a Seven-Coordinate Bipyridine-Bipyrazole Ruthenium(IV) Oxo Complex
Jing Chen1,2, Tingting Yang1, Sushan Feng2
1Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei 230009, P. R. China.
Abstract:
Ruthenium-oxo species with high coordination numbers have long been proposed as active intermediates in catalytic oxidation chemistry. By employing a tetradentate bipyridine-bipyrazole ligand, we herein reported the synthesis of a seven-coordinate (CN7) ruthenium(IV) oxo complex, [RuIV(tpz)(pic)2(O)]2+ (RuO) (tpz = 6,6'-di(1H-pyrazol-1-yl)-2,2'-bipyridine, pic = 4-picoline), which exhibits high activity toward the oxidation of alkylaromatic hydrocarbons. The large kinetic isotope effects (KIE) for the oxidation of DHA/DHA-d4 (KIE = 10.3 ± 0.1) and xanthene/xanthene-d2 (KIE = 17.2 ± 0.1), as well as the linear relationship between log (rate constants) and bond dissociation energies of alkylaromatics, confirmed a mechanism of hydrogen atom abstraction.
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