C−H Bond Activation by Unsymmetrical 2-(N-Arylimino)pyrrolide Pt Complexes: Geometric Effects on Reactivity

Iverson, Carl N. and Carter, Charles A. G. and Baker, R. Tom and Scollard, John D. and Labinger, Jay A. and Bercaw, John E. (2003) C−H Bond Activation by Unsymmetrical 2-(N-Arylimino)pyrrolide Pt Complexes: Geometric Effects on Reactivity. Journal of the American Chemical Society, 125 (42). pp. 12674-12675. ISSN 0002-7863. doi:10.1021/ja036511d. https://resolver.caltech.edu/CaltechAUTHORS:20170405-141647841

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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.

Item Type:

Article

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URL	URL Type	Description
http://dx.doi.org/10.1021/ja036511d	DOI	Article
http://pubs.acs.org/doi/suppl/10.1021/ja036511d	Publisher	Supporting Information

ORCID:

Author	ORCID
Labinger, Jay A.	0000-0002-1942-9232

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.

Funders:

Funding Agency	Grant Number
Akzo-Nobel	UNSPECIFIED
Department of Energy (DOE)	UNSPECIFIED
Los Alamos National Laboratory	UNSPECIFIED
BP	UNSPECIFIED

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DOI:

10.1021/ja036511d

Record Number:

CaltechAUTHORS:20170405-141647841

Persistent URL:

https://resolver.caltech.edu/CaltechAUTHORS:20170405-141647841

Official Citation:

C−H Bond Activation by Unsymmetrical 2-(N-Arylimino)pyrrolide Pt Complexes: Geometric Effects on Reactivity Carl N. Iverson, Charles A. G. Carter, R. Tom Baker, John D. Scollard, Jay A. Labinger, and John E. Bercaw, Journal of the American Chemical Society 2003 125 (42), 12674-12675 DOI: 10.1021/ja036511d

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ID Code:

75741

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CaltechAUTHORS

Deposited By:

Tony Diaz

Deposited On:

05 Apr 2017 21:47

Last Modified:

15 Nov 2021 16:36

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