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The free-energy barrier to hydride transfer across a dipalladium complex
Citation
Vanston, CR and Kearley, GJ and Edwards, AJ and Darwish, TA and de Souza, NR and Ramirez-Cuesta, AJ and Gardiner, MG, The free-energy barrier to hydride transfer across a dipalladium complex, Faraday Discussions, 177 pp. 99-109. ISSN 1359-6640 (2015) [Refereed Article]
Copyright Statement
© The Royal Society of Chemistry 2015
Abstract
We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd–Pd–H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium hydride [{(MesIm)2CH2}2Pd2H][PF6], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol−1 with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model for the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique.
Item Details
Item Type: | Refereed Article |
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Research Division: | Chemical Sciences |
Research Group: | Inorganic chemistry |
Research Field: | Organometallic chemistry |
Objective Division: | Expanding Knowledge |
Objective Group: | Expanding knowledge |
Objective Field: | Expanding knowledge in the chemical sciences |
UTAS Author: | Vanston, CR (Ms Catriona Vanston) |
UTAS Author: | Gardiner, MG (Associate Professor Michael Gardiner) |
ID Code: | 102510 |
Year Published: | 2015 |
Funding Support: | Australian Research Council (DP120101540) |
Web of Science® Times Cited: | 5 |
Deposited By: | Chemistry |
Deposited On: | 2015-08-25 |
Last Modified: | 2017-11-02 |
Downloads: | 0 |
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