ja8b04470_si_004.cif (46.17 kB)
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
dataset
posted on 2018-05-21, 04:30 authored by Ka-Pan Shing, Bei Cao, Yungen Liu, Hung Kay Lee, Ming-De Li, David Lee Phillips, Xiao-Yong Chang, Chi-Ming CheThe 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)].