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C-H and O2 Activation at a Pt(II) Center Enabled by a Novel Sulfonated CNN Pincer Ligand.
- Source :
-
Organometallics . Jan2017, Vol. 36 Issue 1, p207-219. 13p. - Publication Year :
- 2017
-
Abstract
- A novel sulfonated CNN pincer ligand has been designed to support CH and O2 activation at a Pt(II) center. The derived cycloplatinated aqua complex <bold>7</bold> 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 °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 <bold>7</bold> reacts slowly in TFE solutions under ambient light but not in the dark with O2 to selectively produce a Pt(IV) trifluoroethoxo derivative. The H/D exchange reaction kinetics and results of the DFT study suggest that complex <bold>7</bold>, 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. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 02767333
- Volume :
- 36
- Issue :
- 1
- Database :
- Academic Search Index
- Journal :
- Organometallics
- Publication Type :
- Academic Journal
- Accession number :
- 120677274
- Full Text :
- https://doi.org/10.1021/acs.organomet.6b00613