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First principles static and dynamic calculations for the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3)
Sieffert, Nicolas; Kendrick, Thomas; Tiana, Davide; Morrison, Carole A.
We present a first principles static and dynamical study of the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3), with a view to arriving at an understanding of how the variation in the electronic properties of the metal sites and ligands can influence the dynamics of the resulting complexes. A broad range of behaviour was observed, encompassing stable classical minima (M = Os, L = NH3 and M = Ru, L = PH3) to stable eta(2)-H-2 non-classical minima (M = Fe, L = PF3 and M = Ru, L = PH3 or PF3), with the other structures exhibiting dynamical behaviour that spontaneously converted between the classical and non-classical states during the molecular dynamics simulations. The importance of a small L-axial-M-L-axial angle in stabilising the non-classical state is highlighted, as is a short eta(2)-H-2 center dot center dot center dot H-cis distance in non-classical complexes that spontaneously convert to the classical form. We also investigated the changes in the electronic structure of the complex FeH4(PH3)(3) during a eta(2)-H-2 bond breaking/bond making reaction and observed direct evidence of the 'cis effect', whereby a neighbouring hydride ligand acts to stabilise the intermediate classical state.
Keyword(s): Interacting quantum atoms; Complexes; Hydrogen; Pseudopotentials; Distributions; Localization; Equilibrium; Reactivity; Dihydrogen; Molecules; Hydrides; Calculations; Complexation; Electronic properties; Electronic structure; Iron compounds; Ligands; Molecular dynamics; Osmium; Reaction intermediates
Publication Date:
2015
Type: Journal article
Peer-Reviewed: Yes
Language(s): English
Institution: University College Cork
Citation(s): Sieffert, N., Kendrick, T., Tiana, D. and Morrison, C. A. (2015) 'First principles static and dynamic calculations for the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3)', Dalton Transactions, 44(9), pp. 4259-4270. doi: 10.1039/c4dt02475c
Publisher(s): Royal Society of Chemistry (RSC)
File Format(s): application/pdf
First Indexed: 2018-07-06 06:30:38 Last Updated: 2018-07-06 06:30:38