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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.
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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.
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Keyword(s):
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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:
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2015 |
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Type:
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Journal article |
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Peer-Reviewed:
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Yes |
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Language(s):
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English |
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Institution:
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University College Cork |
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Citation(s):
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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 |
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Publisher(s):
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Royal Society of Chemistry (RSC) |
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File Format(s):
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application/pdf |
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First Indexed:
2018-07-06 06:30:38 Last Updated:
2018-07-06 06:30:38 |
