Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2015-04-16

Comparing the energetic and dynamic contributions of solvent to very low barrier isomerization using dynamic steady-state vibrational spectroscopy.

Andrea N Giordano, Benjamin J Lear

Index: J. Phys. Chem. A 119(15) , 3545-55, (2015)

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Abstract

We report the solvent-dependent dynamics of carbonyl site exchange for Fe(CO)3(η(4)-norbornadiene) (FeNBD) in a series of linear and nonlinear alkanes. The barrier to exchange is very low (∼1.5 kcal/mol), and the resulting carbonyl dynamics are rapid enough to lead to a change in the vibrational spectra, which we use to extract the ultrafast rates of exchange from linear Raman spectra of FeNBD. The dynamics of the carbonyl exchange has a weak dependence upon the solvent, and we analyze this dependence in terms of energetic (reaction field) and dynamic (Kramers theory) models of solvent effects. We find that both models can reproduce the observed solvent dependence but that the dynamic model provides a more physically satisfying picture for the solvent effects than does the energetic model. Finally, we find that cyclohexane is more strongly coupled to the dynamics of FeNBD than are the noncyclic alkanes.