Chaplin, Adrian B., Poblador-Bahamonde, Amalia I., Sparkes, Hazel A., Howard, J. A. K., Macgregor, Stuart A. and Weller, Andrew S.. (2009) Alkyl dehydrogenation in a Rh(i) complex via an isolated agostic intermediate. Chemical Communications (No.2). pp. 244-246. ISSN 1359-7345

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Abstract

A well-characterised 14-electron rhodium phosphine complex, [Rh(P(i)Pr(3))(3)][BAr(4)(F)], which contains a beta-CH agostic interaction, is observed to undergo spontaneous dehydrogenation to afford [Rh(P(i)Pr(3))(2)(P(i)Pr(2)(C(3)H(5)))][BAr(4)(F)]; calculations on a model system show that while C-H activation is equally accessible from the beta-CH agostic species or an alternative gamma-CH agostic isomer, subsequent beta-H-transfer can only be achieved along pathways originating from the beta-CH agostic form.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH):	Transition metal catalysts, Rhodium, Dehydrogenation, Alkenes
Journal or Publication Title:	Chemical Communications
Publisher:	Royal Society of Chemistry
ISSN:	1359-7345
Date:	8 January 2009
Number:	No.2
Page Range:	pp. 244-246
Identification Number:	10.1039/b816739g
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
References:	1 (a) C. M. Jensen, Chem. Commun., 1999, 2443; (b) R. H. Crabtree, J. Chem. Soc., Dalton Trans., 2001, 2437; (c) A. S. Goldman, A. H. Roy, Z. Huang, R. Ahuja, W. Schinski and M. Brookhart, Science, 2006, 312, 257. 2 (a) G. J. Kubas, Metal Dihydrogen and s-Bond Complexes, Kluwer Academic/Plenum Publishers, New York, 2001; (b) M. Brookhart, M. L. H. Green and G. Parkin, Proc. Natl. Acad. Sci. U. S. A., 2007, 104, 6908. 3 N. M. Scott, R. Dorta, E. D. Stevens, A. Correa, L. Cavallo and S. P. Nolan, J. Am. Chem. Soc., 2005, 127, 3516. 4 (a) A. C. Albeniz, G. Schulte and R. H. Crabtree, Organometallics, 1992, 11, 242; (b) B. Rybtchinski, L. Konstantinovsky, L. J. W. Shimon, A. Vigalok and D. Milstein, Chem.–Eur. J., 2000, 6, 3287; (c) D. Buccella and G. Parkin, J. Am. Chem. Soc., 2006, 128, 16358; (d) A. Toner, J. Matthes, S. Gruendemann, H. Limbach, B. Chaudret, E. Clot and S. Sabo-Etienne, Proc. Natl. Acad. Sci. U. S. A., 2007, 104, 6945; (e) L. Mole, J. L. Spencer, N. Carr and A. G. Orpen, Organometallics, 1991, 10, 49. 5 M. Baya,M.L.Buil, M. A. Esteruelas andE.Onate, Organometallics, 2004, 23, 1416–1423. 6 P. B. Glaser and T. D. Tilley, Organometallics, 2004, 23, 5799. 7 A. J. Edwards,M. A. Esteruelas, F. J. Lahoz, A.M. Lopez, E.Onate, L. A. Oro and J. I. Tolosa, Organometallics, 1997, 16, 1316. 8 (a) D. L. Thorn, Organometallics, 1998, 17, 348; (b) N. Thirupathi, D. Amoroso, A. Bell and J. D. Protasiewicz, Organometallics, 2005, 24, 4099. 9 M. J. Ingleson, M. F. Mahon and A. S. Weller, Chem. Commun., 2004, 2398. 10 S. Brayshaw, J. Green, G. Kociok-Ko¨ hn, E. Sceats and A. S. Weller, Angew. Chem., Int. Ed., 2006, 45, 452. 11 W. Baratta, C. Mealli, E. Herdtweck, A. Ienco, S. A. Mason and P. Rigo, J. Am. Chem. Soc., 2004, 126, 5549. 12 (a) H. Urtel, C. Meier, F. Eisentrager, F. Rominger, J. P. Joschek and P. Hofmann, Angew. Chem., Int. Ed., 2001, 40, 781; (b) P. H. M. Budzelaar, N. N. P. Moonen, R. de Gelder, J. M. M. Smits and A. W. Gal, Eur. J. Inorg. Chem., 2000, 753; (c) W. Baratta, S. Stoccoro, A. Doppiu, E. Herdtweck, A. Zucca and P. Rigo, Angew. Chem., Int. Ed., 2003, 42, 105; (d) A. Y. Verat, M. Pink, H. Fan, J. Tomaszewski and K. G. Caulton, Organometallics, 2008, 27, 166, and references therein. 13 Y. W. Yared, S. L. Miles, R. Bau and C. A. Reed, J. Am. Chem. Soc., 1977, 99, 7076. 14 H. Aneetha, M. Jimenez-Tenorio, M. C. Puerta, P. Valerga, V. N. Sapunov, R. Schmid, K. Kirchner and K. Mereiter, Organometallics, 2002, 21, 5334. 15 A. C. Cooper, E. Clot, J. C. Huffman, W. E. Streib, F. Maseras, O. Eisenstein and K. G. Caulton, J. Am. Chem. Soc., 1999, 121, 97–106. 16 (a) T. M. Douglas and A. S. Weller, New J. Chem., 2008, 32, 966; (b) T. M. Douglas, S. K. Brayshaw, R. Dallanegra, G. Kociok-Ko¨ hn, S. A. Macgregor, G. Moxham, A. S. Weller, T. Wondimagegn and P. Vadivelu, Chem.–Eur. J., 2008, 14, 1004; (c) T. M. Douglas, H. Le Notre, S. K. Brayshaw, C. G. Frost and A. S. Weller, Chem. Commun., 2006, 3408. 17 Calculations employed Gaussian 03 with the BP86 functional. Rh and P centres were described with Stuttgart RECPs and basis sets with polarisation on P. 6-31G** basis sets were used for C and H atoms. All energies include a correction for zero-point energies. See ESIw for full details.
URI:	http://wrap.warwick.ac.uk/id/eprint/40533

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