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

Journal of the American Chemical Society

Volumn 128, Issue 23, 2006, Pages 7452-7453

  Ampt, Kirsten A M ^a   Burling, Suzanne ^b   Donald, Steven M A ^c   Douglas, Susie ^b   Duckett, Simon B ^a   Macgregor, Stuart A ^c   Perutz, Robin N ^a   Whittlesey, Michael K ^b  

^a UNIVERSITY OF YORK   (United Kingdom)

^b University of Bath Claverton Down   (United Kingdom)

^c HERIOT WATT UNIVERSITY   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

CARBENE; HETEROCYCLIC COMPOUND; HYDROGEN; RUTHENIUM COMPLEX;

ARTICLE; CHEMICAL REACTION KINETICS; DENSITY FUNCTIONAL THEORY; ISOMERIZATION; MOLECULAR STABILITY; PHOSPHORUS NUCLEAR MAGNETIC RESONANCE; PHOTOCHEMISTRY; PHOTOLYSIS; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; ULTRAVIOLET IRRADIATION;

EID: 33745017394     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0622397     Document Type: Article

References (16)

1. Scott, N. M.; Nolan, S. P. Eur. J. Inorg. Chem. 2005, 10, 1815.
2. Grubbs, R. H. Tetrahedron 2004, 60, 7117.
3. Burling, S.; Mahon, M. F.; Paine, M. F.; Whittlesey, M. K.; Williams, J. M. J. Organometallics 2004, 23, 4537.
4. (a) Geoffroy, G. L.; Bradley, M. G. Inorg. Chem. 1977, 16, 744.
5. (b) Colombo, M.; George, M. W.; Moore, J. N.; Pattison, D. I.; Perutz, R. N.; Virrels, I. G.; Ye, T.-Q. J. Chem. Soc., Dalton Trans. 1997, 2857.
6. A different isomer of this C-H activated complex is reported in ref 3.
7. Frisch, M.; et al.; Gaussian 98, revision A. 11.4; Gaussian, Inc.: Pittsburgh, PA, 2001. Calculations used the BP86 functional, Ru and P were described with Stuttgart RECPs and associated basis sets. 6-31G** basis sets were used for all other atoms, with the exception of phosphine groups, where 6-31G was employed. Energies include corrections for zero-point energy. See Supporting Information for details.
8. Since enhancement of the hydride signals in 3 results from their origin in a second-order spin system, its proportion cannot be estimated.
9. 2.
10. (a) Bruno, J. W.; Huffman, J. C.; Green, M. A.; Zubkowski, J. D.; Hatfield, W. E.; Caulton, K. G. Organometallics 1990, 9, 2556.
11. (b) Montiel-Palma, V.; Perutz, R. N.; George, M. W.; Jina, O. S.; Sabo-Etienne, S. Chem. Commun. 2000, 1175.
12. 2-dihydrogen signals is consistent with exchange as seen in closely related complexes. See: Giunta, K. D.; Holscher, M.; Lehmann, C. W.; Mynott, R.; Wirtz, C.; Leitner, W. Adv. Synth. Catal. 2003, 345, 1139.
13. 2 enhancement.
14. Dunne, J. P.; Blazina, D.; Aiken, S.; Carteret, H. A.; Duckett, S. B.; Jones, J. A.; Poli, R.; Whitwood, A. C. Dalton Trans. 2004, 3616.
15. 3 loss from 1 is +34 kcal/mol.
16. Baker, M. V.; Field, L. D. J. Am. Chem. Soc. 1987, 109, 2825.