Photochemistry of (η 6-anisole)Cr(CO) 3 and (η 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

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

Research output: Journal PublicationArticlepeer-review

11 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)962-969
Number of pages8
JournalJournal of Physical Chemistry A
Volume116
Issue number3
DOIs
Publication statusPublished - 26 Jan 2012
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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