Arylruthenium(III)
Porphyrin-Catalyzed C–H
Oxidation and Epoxidation at Room Temperature and [RuV(Por)(O)(Ph)]
Intermediate by Spectroscopic Analysis and Density Functional Theory
Calculations
Posted on 2018-05-21 - 04:30
The development of
highly active and selective metal catalysts
for efficient oxidation of hydrocarbons and identification of the
reactive intermediates in the oxidation catalysis are long-standing
challenges. In the rapid hydrocarbon oxidation catalyzed by ruthenium(IV)
and -(III) porphyrins, the putative Ru(V)-oxo intermediates remain
elusive. Herein we report that arylruthenium(III) porphyrins are highly
active catalysts for hydrocarbon oxidation. Using catalyst [RuIII(TDCPP)(Ph)(OEt2)] (H2TDCPP = 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin),
the oxidation of C–H bonds of various hydrocarbons with oxidant m-CPBA at room temperature gave alcohols/ketones in up to
99% yield within 1 h; use of [nBu4N]IO4 as a mild alternative oxidant avoided formation
of lactone from cyclic ketone in C–H oxidation, and the catalytic
epoxidation with up to 99% yield and high selectivity (no aldehydes
as side product) was accomplished within 5 min. UV–vis, electrospray
ionization–mass spectrometry, resonance Raman, electron paramagnetic
resonance, and kinetic measurements and density functional theory
calculations lend evidence for the formation of Ru(V)-oxo intermediate
[RuV(TDCPP)(O)(Ph)].
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Shing, Ka-Pan; Cao, Bei; Liu, Yungen; Lee, Hung Kay; Li, Ming-De; Phillips, David Lee; et al. (2018). Arylruthenium(III)
Porphyrin-Catalyzed C–H
Oxidation and Epoxidation at Room Temperature and [RuV(Por)(O)(Ph)]
Intermediate by Spectroscopic Analysis and Density Functional Theory
Calculations. ACS Publications. Collection. https://doi.org/10.1021/jacs.8b04470
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AUTHORS (8)
KS
Ka-Pan Shing
BC
Bei Cao
YL
Yungen Liu
HL
Hung Kay Lee
ML
Ming-De Li
DP
David Lee Phillips
XC
Xiao-Yong Chang
CC
Chi-Ming Che