Journal
ORGANOMETALLICS
Volume 36, Issue 1, Pages 207-219Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.6b00613
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Funding
- National Science Foundation [CHE-1464772]
- Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0001298]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1464772] Funding Source: National Science Foundation
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A novel sulfonated CNN pincer ligand has been designed to support CH and O-2 activation at a Pt(II) center. The derived cycloplatinated aqua complex 7 was found to be one of the most active reported homogeneous Pt catalysts for H/D exchange between studied arenes (benzene, benzene-d(6), toluene-d(8), p-xylene, and mesitylene) and 2,2,2-trifluoroethanol (TFE) or 2,2,2-trifluoroethanol-d; the TON for C6D6 as a substrate is >250 after 48 h at 80 degrees C. The reaction is very selective; no benzylic CH bond activation was observed. The per-CH-bond reactivity diminishes in the series benzene (19) > toluene (p-CH:m-CH:o-CH = 1:0.9:0.2) > xylene (2.9) > mesitylene (1.1). The complex 7 reacts slowly in TFE solutions under ambient light but not in the dark with O-2 to selectively produce a Pt(IV) trifluoroethoxo derivative. The H/D exchange reaction kinetics and results of the DFT study suggest that complex 7, and not its TFE derivatives, is the major species responsible for the arene CH bond activation. The reaction deuterium kinetic isotope effect, k(H)/k(D) = 1.7, the reaction selectivity, and reaction kinetics modeling suggest that the CH bond cleavage step is rate-determining.
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