Keith, John A. and Oxgaard, Jonas and Goddard, William A., III (2006) Inaccessibility of β-Hydride Elimination from −OH Functional Groups in Wacker-Type Oxidation. Journal of the American Chemical Society, 128 (10). pp. 3132-3133. ISSN 0002-7863. doi:10.1021/ja0533139. https://resolver.caltech.edu/CaltechAUTHORS:20170427-082648149
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Abstract
Quantum mechanics calculations (B3LYP and MPW1K density functional theory) on mechanisms relevant to the Wacker process for dehydrogenation of alcohol to ketone show that the commonly accepted mechanism for product formation (β-hydride elimination (BHE) leading to Pd−H formation) is not energetically feasible (36.2 kcal/mol). An alterative pathway involving a five-bodied reductive elimination (RE) leads to an activation enthalpy of 18.8 kcal/mol, which is just half that of the BHE from the −OH group usually assumed for the Wacker process. We find that a water molecule catalyzes both processes, reducing the barrier to 17.2 for RE and 25.0 for BHE, but will not change the relative ordering of the two mechanisms. This suggests that assumptions of BHE mechanisms should be reexamined for cases in which the β atom is not an alkyl group.
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| Additional Information: | © 2006 American Chemical Society. Received May 20, 2005; Revised Manuscript Received November 1, 2005. Publication Date (Web): February 18, 2006. J.A.K. expresses his gratitude to G. O. Spessard, R. J. Nielsen, and J. S. Su for helpful discussions and insight. This research was partially supported by the Chevron-Texaco Energy Research and Technology Company. | |||||||||
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| Issue or Number: | 10 | |||||||||
| DOI: | 10.1021/ja0533139 | |||||||||
| Record Number: | CaltechAUTHORS:20170427-082648149 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20170427-082648149 | |||||||||
| Official Citation: | Inaccessibility of β-Hydride Elimination from −OH Functional Groups in Wacker-Type Oxidation John A. Keith, Jonas Oxgaard, and William A. Goddard, III Journal of the American Chemical Society 2006 128 (10), 3132-3133 DOI: 10.1021/ja0533139 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 76980 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Tony Diaz | |||||||||
| Deposited On: | 27 Apr 2017 16:37 | |||||||||
| Last Modified: | 15 Nov 2021 17:04 |
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