C−H Bond Activation by Unsymmetrical 2-(N-Arylimino)pyrrolide Pt Complexes: Geometric Effects on Reactivity
Abstract
Reactions of chloroplatinum methyl complexes with N-(arylimino)pyrrolide anions afford cis and trans neutral platinum methyl complexes. Isomers with methyl trans to the pyrrolide nitrogen activate benzene C−H bonds at 85 °C more than 80 times faster than the corresponding cis isomer. In addition, reactions of platinum dimethyl complexes with N-(arylimino)pyrroles (Ar = 4-substituted phenyl) in C_6D_6 at ambient temperature give unlabeled methane and cis methyl complex containing heavily deuterated Pt−Me. In contrast, bulky aryl substituents give methane isotopomers and trans-Pt−Ph product. The origins of these observations are discussed.
Additional Information
© 2003 American Chemical Society. Received June 4, 2003; Publication Date (Web): September 24, 2003. Parts of this work were supported by Akzo-Nobel; a joint DOE-OIT grant; the Los Alamos LDRD program; and BP. We thank Ulrich Fekl and Dave Thorn for helpful discussions. J.D.S. thanks Larry Henling and the X-ray Crystallography Facility of the Beckman Institute at Caltech for assistance with crystal structure determinations.Attached Files
Supplemental Material - ja036511dsi20030610_080743.cif
Supplemental Material - ja036511dsi20030610_081111.cif
Supplemental Material - ja036511dsi20030807_095401.pdf
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Additional details
- Eprint ID
- 75741
- Resolver ID
- CaltechAUTHORS:20170405-141647841
- Akzo-Nobel
- Department of Energy (DOE)
- Los Alamos National Laboratory
- BP
- Created
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2017-04-05Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field