Photochemical isomerization of N-heterocyclic carbene ruthenium hydride complexes: in situ photolysis, parahydrogen, and computational studies

Kirsten A M Ampt; Suzanne Burling; Steven M A Donald; Susie Douglas; Simon B Duckett; Stuart A Macgregor; Robin N Perutz; Michael K Whittlesey

doi:10.1021/ja0622397

Photochemical isomerization of N-heterocyclic carbene ruthenium hydride complexes: in situ photolysis, parahydrogen, and computational studies

J Am Chem Soc. 2006 Jun 14;128(23):7452-3. doi: 10.1021/ja0622397.

Authors

Kirsten A M Ampt¹, Suzanne Burling, Steven M A Donald, Susie Douglas, Simon B Duckett, Stuart A Macgregor, Robin N Perutz, Michael K Whittlesey

Affiliation

¹ Department of Chemistry, University of York, Heslington, York YO10 5DD, UK.

PMID: 16756294
DOI: 10.1021/ja0622397

Abstract

Low-temperature UV irradiation of the N-heterocyclic carbene complex Ru(IEt2Me2)(PPh3)2(CO)H2 (IEt2Me2 = 1,3-bis(ethyl)-4,5-dimethylimidazol-2-ylidene) leads to a remarkable photoisomerization reaction. By combining in situ photolysis and parahydrogen experiments to characterize the ultimate photoproducts and DFT calculations to interrogate the structures of the key 16-electron intermediates, the importance of both PPh3 and H2 loss pathways has been established.