A Caltech Library Service

Mechanism of Direct Molecular Oxygen Insertion in a Palladium(II)−Hydride Bond

Keith, Jason M. and Muller, Richard P. and Kemp, Richard A. and Goldberg, Karen I. and Goddard, William A., III and Oxgaard, Jonas (2006) Mechanism of Direct Molecular Oxygen Insertion in a Palladium(II)−Hydride Bond. Inorganic Chemistry, 45 (24). pp. 9631-9633. ISSN 0020-1669. doi:10.1021/ic061392z.

[img] PDF - Supplemental Material
See Usage Policy.


Use this Persistent URL to link to this item:


The mechanism of the direct insertion of molecular oxygen into a palladium hydride bond has been elucidated using quantum mechanics (B3LYP/LACVP^(**) with the PBF continuum solvent model). The key step is found to be the abstraction of the hydrogen atom resulting in the formation of a Pd^I/HO_2 (triplet) radical pair, which then proceeds to form a singlet palladium hydroperoxo species. Potential palladium(0) pathways were explored and were found to be inaccessible. The results are in agreement with recent experimental results and are consistent with our previously predicted mechanism for an analogue system.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Keith, Jason M.0000-0002-5292-397X
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2006 American Chemical Society. Received 25 July 2006. Published online 1 November 2006. Published in print 1 November 2006. J.M.K. thanks the National Science Foundation for financial support. The personnel involved in this research were partially supported by DOE (Grant DE-PS36-03GO93015), ONR (Grant N00014-06-1-0938), and ChevronTexaco. The facilities used were funded by grants from ARO-DURIP and ONR-DURIP. R.A.K. and K.I.G. acknowledge funding from DOE Grant DE-FG02-06ER15765. Sandia National Laboratories is a multiprogram laboratory operated by Sandia Corp., a Lockheed Martin Co., for the United States Department of Energy under Contract DE-AC04-94AL85000.
Funding AgencyGrant Number
Department of Energy (DOE)DE-PS36-03GO93015
Office of Naval Research (ONR)N00014-06-1-0938
Army Research Office (ARO)UNSPECIFIED
Department of Energy (DOE)DE-FG02-06ER15765
Department of Energy (DOE)DE-AC04-94AL85000
Issue or Number:24
Record Number:CaltechAUTHORS:20170425-094948518
Persistent URL:
Official Citation:Mechanism of Direct Molecular Oxygen Insertion in a Palladium(II)−Hydride Bond Jason M. Keith, Richard P. Muller, Richard A. Kemp, Karen I. Goldberg, William A. Goddard, III, and Jonas Oxgaard Inorganic Chemistry 2006 45 (24), 9631-9633 DOI: 10.1021/ic061392z
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76905
Deposited By: Ruth Sustaita
Deposited On:25 Apr 2017 19:26
Last Modified:15 Nov 2021 17:03

Repository Staff Only: item control page