Logo of Science Foundation Ireland  Logo of the Higher Education Authority, Ireland7 Capacities
Ireland's High-Performance Computing Centre | ICHEC
Home | News | Infrastructure | Outreach | Services | Research | Support | Education & Training | Consultancy | About Us | Login


Title:Photochemistry of (eta(6)-Anisole)Cr(CO)(3) and (eta(6)-Thioanisole)Cr(CO)(3): Evidence for a Photoinduced Haptotropic Shift of the Thioanisole Ligand, a Picosecond Time-Resolved Infrared Spectroscopy and Density Functional Theory Investigation
Authors:Clark, Ian P. George, Michael W. Greetham, Gregory M. Harvey, Emma C. Long, Conor Manton, Jennifer C. McArdle, Hazel Pryce, Mary T., 2012
Abstract: The photochemistry of (eta(6)-anisole)Cr(CO)(3) and (eta(6)-thioanisole)Cr(CO)(3) was investigated by picosecond time-resolved infrared spectroscopy in n-heptane solution at 298 K. Two independent excited states are populated following 400 rim excitation of each of these complexes. An excited state with some metal-to-CO charge-transfer character is responsible for the CO-loss process, which is slow compared to CO-loss from Cr(CO)(6). Observed first order rate constants of 1.8 x 10(10) s(-1) and 2.5 x 10(1)0 s(-1) were obtained for the anisole and thioanisole complexes, respectively. The second excited state has metal-to-arene charge transfer character and results in a haptotropic shift of the thioanisole ligand. DFT calculations characterized the excited states involved and the nature of the haptotropic shift intermediate observed for the thioanisole species.
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, Volume 116, Issue 3 p 962-969
URL: http://pubs.acs.org/doi/abs/10.1021/jp211726j
Status: Published

return to publications list