| 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
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| 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 |
