Keith, Jason M. and Nielsen, Robert J. and Oxgaard, Jonas and Goddard, William A., III (2005) Pd-Mediated Activation of Molecular Oxygen in a Nonpolar Medium. Journal of the American Chemical Society, 127 (38). pp. 13172-13179. ISSN 0002-7863. doi:10.1021/ja043094b. https://resolver.caltech.edu/CaltechAUTHORS:20170420-063814391
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Abstract
The mechanism for direct insertion of O_2 in a toluene-solvated palladium−hydride bond (avoiding palladium zero) has been elucidated using quantum mechanics (B3LYP/LACVP^(**) with the PBF polarizable continuum solvent model) for Pd^(II)((−)-sparteine)(Cl)(H) and the model compound PdII(bipyridine)(Cl)(H). We find that the process involves (1) the abstraction of the hydrogen atom by triplet oxygen, (2) the formation of a stable L_2XPd^IOOH triplet species, (3) a spin transition resulting in a stable L_2XPd^(II)OOH singlet species, and (4) the loss of H_2O_2 and completion of the catalytic cycle upon the addition of HX. The limitations involved in the spin transition, the formation of the triplet Pd^I−OOH species and the stability of that triplet species are all dependent on the presence of an H-bond acceptor cis to the hydride and the electronic characteristics of the other ligands which may or may not stabilize the Pd^I species. Without this cis H-bond acceptor and/or electron-withdrawing ligands that can stabilize Pd^I, the reaction will not proceed via the palladium hydride insertion mechanism in a nonpolar environment.
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Additional Information: | © 2005 American Chemical Society. Received 16 November 2004. Published online 2 September 2005. Published in print 28 September 2005. J.M.K. thanks the National Science Foundation for financial support. This research was partly funded by the NSF (CTS-01322002) and ChevronTexaco, and the facilities used were funded by grants from ARO-DURIP, ONR- DURIP, IBM-SUR, and the Beckman Institute. | ||||||||||||||
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Issue or Number: | 38 | ||||||||||||||
DOI: | 10.1021/ja043094b | ||||||||||||||
Record Number: | CaltechAUTHORS:20170420-063814391 | ||||||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20170420-063814391 | ||||||||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||||
ID Code: | 76741 | ||||||||||||||
Collection: | CaltechAUTHORS | ||||||||||||||
Deposited By: | Ruth Sustaita | ||||||||||||||
Deposited On: | 20 Apr 2017 16:28 | ||||||||||||||
Last Modified: | 15 Nov 2021 17:02 |
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