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.

First principles static and dynamic calculations for the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3)

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c4dt02475c.pdf(3.2 MB)

Published version

Date

2015-01-20

Authors

Sieffert, Nicolas

Kendrick, Thomas

Tiana, Davide

Morrison, Carole A.

Publisher

Royal Society of Chemistry (RSC)

Published Version

10.1039/c4dt02475c

Abstract

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.

Keywords

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 , Reaction kinetics , Ruthenium , Transition metal compounds , Transition metals

Citation

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