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Published July 17, 2005 | Supplemental Material
Journal Article Open

Mechanism of C−H Bond Activation of Alkyl-Substituted Benzenes by Cationic Platinum(II) Complexes


While all methyl- and ethyl-substituted benzenes react with diimine Pt(II) methyl cations to give η^3-benzyl products, they do not all get there by the same pathway. For toluene and p-xylene, isotopic labeling shows that initial activation occurs at aryl positions with subsequent intermolecular conversion to the benzyl product. For ethylbenzene and 1,4-diethylbenzene, initial activation takes place exclusively at aryl C−H bonds, and conversion to the η^3-benzyl product takes place via intramolecular isomerization. Only in the most extreme case of steric crowding the reaction of a bulky diimine platinum methyl cation (Ar = Mes) with triethylbenzene does direct activation of the ethyl group become preferred to aryl activation.

Additional Information

© 2005 American Chemical Society. Received April 4, 2005. Publication Date (Web): June 22, 2005. Funding for this work was provided by the bp MC2 program and the NIH in the form of a NRSA fellowship to T.G.D. (GM070272-02). We thank Jonathan S. Owen for insightful discussions, Dr. Scott Ross for assistance with NMR spectrometry, Dr. Mona Shahgholi for mass spectrometry data, and Mr. Larry M. Henling for crystallographic analysis.

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Supplemental Material - om050251msi20050509_053711.pdf


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