Kinetic and Thermodynamic Preferences in Aryl vs Benzylic C−H Bond Activation with Cationic Pt(II) Complexes
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1.
California Institute of Technology
Abstract
Anhydrous cationic Pt(II) complexes [(NN)Pt(CH_3)(CF_3CD_2OD)]+ (1, NN = ArNC(Me)−C(Me)NAr), which are obtained by reaction of (NN)Pt(CH_3)_2 with B(C_6F_5)_3 in CF_3CD_2OD, activate C−H bonds of benzene and methylbenzenes, with enhanced reactivity compared to the previously prepared equilibrium mixtures with the (thermodynamically favored) aquo complexes. For methylbenzenes (toluene, p-xylene, mesitylene), activation at the aromatic and benzylic positions are kinetically competitive, but the product of the latter is strongly favored thermodynamically. This unusual trend is attributed to formation of η^3-benzyl structures, which can be observed spectroscopically for 1,4-diethylbenzene activation.
Additional Information
© 2004 American Chemical Society. Received 16 August 2004. Published online 28 October 2004. Published in print 1 November 2004. Funding for this work was provided by the BP MC2 program and the NIH in the form of an NCI fellowship to A.F.H. and an NRSA fellowship to T.G.D. We thank Dr. Scott Ross for assistance with NMR spectrometry, Dr. Mona Shahgholi for mass spectrometry data, and Mr. Larry M. Henling for crystallographic analysis.Attached Files
Supplemental Material - ja045078ksi20040920_071626.cif
Supplemental Material - ja045078ksi20040921_052524.pdf
Files
ja045078ksi20040921_052524.pdf
Additional details
Identifiers
- Eprint ID
- 76753
- Resolver ID
- CaltechAUTHORS:20170420-084321419
Funding
- BP MC2 program
- NIH Predoctoral Fellowship
- National Cancer Institute
Dates
- Created
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2017-04-20Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field