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 Type:	Refereed Article
Research Division:	Chemical Sciences
Research Group:	Other Chemical Sciences
Research Field:	Organometallic Chemistry
Objective Division:	Expanding Knowledge
Objective Group:	Expanding Knowledge
Objective Field:	Expanding Knowledge in the Chemical Sciences
Author:	Vanston, CR (Ms Catriona Vanston)
Author:	Gardiner, MG (Associate Professor Michael Gardiner)
ID Code:	102510
Year Published:	2015
Funding Support:	Australian Research Council (DP120101540)
Web of Science® Times Cited:	3
Deposited By:	Chemistry
Deposited On:	2015-08-25
Last Modified:	2017-11-02
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