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Photochemistry of (η6-anisole)Cr(CO)3 and (η6-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

Photochemistry of (η6-anisole)Cr(CO)3 and (η6-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

Ian P Clark, Michael W George, Gregory M Greetham, Emma C Harvey, Conor Long, Jennifer C Manton, Hazel McArdle, Mary T Pryce

J Phys Chem A. 2012 Jan 26;116(3):962-9.

PMID: 22204670

Abstract:

The photochemistry of (η(6)-anisole)Cr(CO)(3) and (η(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 nm 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 × 10(10) s(-1) and 2.5 × 10(10) 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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP100685	Thioanisole		100-68-5	Price

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