Competitive Benzene C−H Bond Activation versus Olefin Insertion in a (Monomethyl)palladium(II) β-Diketiminate Complex
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1.
California Institute of Technology
Abstract
The monomethylpalladium(II) complex (COD)Pd(CH_3)Cl (COD = 1,5-cyclooctadiene) is found to undergo both benzene C−H activation and migratory insertion of olefin, with the former faster than the latter, at room temperature in the presence of an anionic β-diketiminate ligand, to yield η^3-(6-R-cyclooctenyl)palladium(II) β-diketiminate (R = methyl or phenyl). The reaction is proposed to take place via the formation of a (monomethyl)palladium(II) β-diketiminate with COD as the fourth ligand, followed by competitive benzene C−H activation and migratory insertion of olefin. The proposed mechanism is supported by density functional theory calculations upon a simplified model system.
Additional Information
© 2009 American Chemical Society. Received March 3, 2009. Publication Date (Web): July 10, 2009. We thank Dr. Michael W. Day and Lawrence M. Henling for performing the X-ray crystallographic analysis. B.-L.L. also thanks George S. Chen for suggestions in preparing the manuscript. This work has been generously supported by BP through the MC2 program. Supporting Information: Detailed experimental and computational data. This material is available free of charge via the Internet at http://pubs.acs.org.Attached Files
Supplemental Material - om900171d_si_001.pdf
Supplemental Material - om900171d_si_002.cif
Files
om900171d_si_001.pdf
Additional details
Identifiers
- Eprint ID
- 15092
- DOI
- 10.1021/om900171d
- Resolver ID
- CaltechAUTHORS:20090817-144813701
Related works
- Describes
- 10.1021/om900171d (DOI)
Funding
- BP MC2 program
Dates
- Created
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2009-09-08Created from EPrint's datestamp field
- Updated
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2021-11-08Created from EPrint's last_modified field