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Publication

Title:Potential Energy Mapping of the Excited-States of (eta(6)-Arene)Cr(CO)(3) Complexes: the Evolution Toward CO-Loss or Haptotropic Shift Processes
Authors:Long, Conor, 2012
Abstract: The potential energy profiles of the optically accessible excited states of two model (η6-arene)Cr(CO)3 systems were explored using Time-Dependent Density Functional Theory. Two photochemical reactions were investigated, CO-loss and the haptotropic or ring-slip of the arene ligand. In both cases the photochemical reaction requires the surmounting of a small thermal barrier in the lowest energy excited state. In the case of (η6-benzene)Cr(CO)3 only one excited state is populated following 400 nm excitation and this leads to the release of CO. The calculated energy barrier to this process is 13 kJ mol–1. In the case of (η6-thiophenol)Cr(CO)3 two excited states are accessible one leading to CO-loss while the other results in the ring-slip process. The calculated barrier to the ring-slip process is 11 kJ mol–1. The calculations are consistent with the results of picosecond time-resolved infrared studies.
ICHEC Project:Estimating the potential energy surfaces around pi-coordinated arene ligands in (eta-Arene)Cr(CO)3 complexes
Publication:JOURNAL OF PHYSICAL CHEMISTRY A, 2012, 116 (25), pp 6845–6850
URL: http://pubs.acs.org/doi/abs/10.1021%2Fjp301118v
Status: Published

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