A Caltech Library Service

Pd-Mediated Activation of Molecular Oxygen in a Nonpolar Medium

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.

[img] PDF - Supplemental Material
See Usage Policy.

[img] PDF - Supplemental Material
See Usage Policy.


Use this Persistent URL to link to this item:


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.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Keith, Jason M.0000-0002-5292-397X
Nielsen, Robert J.0000-0002-7962-0186
Goddard, William A., III0000-0003-0097-5716
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.
Funding AgencyGrant Number
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Issue or Number:38
Record Number:CaltechAUTHORS:20170420-063814391
Persistent URL:
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76741
Deposited By: Ruth Sustaita
Deposited On:20 Apr 2017 16:28
Last Modified:15 Nov 2021 17:02

Repository Staff Only: item control page