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. https://resolver.caltech.edu/CaltechAUTHORS:20170425-094948518

PDF - Supplemental Material
See Usage Policy.
24kB

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20170425-094948518

Abstract

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:

URL	URL Type	Description
http://dx.doi.org/10.1021/ic061392z	DOI	Article
http://pubs.acs.org/doi/suppl/10.1021/ic061392z	Publisher	Supporting Information

ORCID:

Author	ORCID
Keith, Jason M.	0000-0002-5292-397X
Goddard, William A., III	0000-0003-0097-5716

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.

Funders:

Funding Agency	Grant Number
Department of Energy (DOE)	DE-PS36-03GO93015
Office of Naval Research (ONR)	N00014-06-1-0938
ChevronTexaco	UNSPECIFIED
Army Research Office (ARO)	UNSPECIFIED
Department of Energy (DOE)	DE-FG02-06ER15765
Department of Energy (DOE)	DE-AC04-94AL85000

Issue or Number:

DOI:

10.1021/ic061392z

Record Number:

CaltechAUTHORS:20170425-094948518

Persistent URL:

https://resolver.caltech.edu/CaltechAUTHORS:20170425-094948518

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

Collection:

CaltechAUTHORS

Deposited By:

Ruth Sustaita

Deposited On:

25 Apr 2017 19:26

Last Modified:

15 Nov 2021 17:03

Repository Staff Only: item control page