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Published November 27, 2006 | Version Supplemental Material
Journal Article Open

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

Creators

  • 1. ROR icon California Institute of Technology
  • 2. ROR icon University of Washington

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.

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.

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Additional details

Identifiers

Eprint ID
76905
Resolver ID
CaltechAUTHORS:20170425-094948518

Funding

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

Dates

Created
2017-04-25
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Updated
2021-11-15
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