Abstract
CLEAVAGE of carbon–carbon bonds by transition-metal-containing heterogeneous catalysts forms the basis of one of the most important industrial processes, the refining of petroleum to chemicals and fuels1. But the generally low product selectivity observed with heterogeneous systems is a significant drawback. For this reason, much effort has been devoted to developing transition-metal complexes that can be inserted into C–C bonds in homogeneous media, as such catalysts can operate under mild, easily controlled conditions and might offer high selectivity and reactivity. Metal insertion into C–H bonds is well known2,3–5, but, except in a few special cases2,6–12, C–C bonds are generally unreactive towards insertion of transition metals in solution. Here we report the selective activation of a simple C–C bond by a mononuclear rhodium complex in a neutral homogeneous medium (tetrahydrofuran solution). We are able to effect Rh insertion into a C–C bond in a diphosphinoxylene, in which this bond is favourably oriented towards the transition-metal centre. The competing reaction of insertion into C–H is suppressed by the use of an overpressure of H2. We suggest that this approach might lead to a general strategy for C–C activation in homogeneous systems.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Sinflet, J. H. in Catalysis: Science and Technology Vol. 1 (eds Anderson, J. R. & Boudart, M.) 257–300 (Springer, New York, 1981).
Crabtree, R. H. Chem. Rev. 85, 245–269 (1985).
Bergman, R. G. Science 223, 902–908 (1984).
Shilov, A. E. Activation of Saturated Hydrocarbons by Transition Metal Complexes (Reidal, Boston, 1984).
Maugh, T. H. Science 220, 1262–1263 (1983).
Periana, R. A. & Bergman, R. G. J. Am. chem. Soc. 108, 7346–7355 (1986).
Crabtree, R. H., Dion, R. P., Gibboni, D. J., McGrath, D. V. & Holt, E. M. J. Am. chem. Soc. 108, 7222–7227 (1986).
Kang, J. W., Moseley, R. & Maitlis, D. M. J. Am. chem. Soc. 91, 5970–5977 (1969).
Benfield, F. W. C. & Green, M. L. H. J. chem. Soc. Dalton Trans. 1324–1331 (1974).
Eilbracht, P. Chem. Ber. 113, 542–554 (1980).
Suggs, J. W. & Jun, C.-H. J. Am. chem. Soc. 106, 3054–3056 (1984).
Hartwig, J. F., Anderson, R. A. & Bergman, R. G. J. Am. chem. Soc. 111, 2717–2719 (1989).
Watson, P. L. & Roe, D. C. J. Am. chem. Soc. 104, 6471–6473 (1982).
Bunel, E., Burger, B. J. & Bercaw, J. E. J. Am. chem. Soc. 110, 976–978 (1988).
Moulton, C. J. & Shaw, B. L. J. chem. Soc. Dalton Trans. 1020–1024 (1976).
Rimml, H. & Venanzi, L. M. J. Organomet. Chem. 259, C6–C7 (1983).
Nemeh, S., Jensen, C., Binamira-Soriaga, E. & Kaska, W. C. Organometallics 2, 1442–1447 (1983).
Milstein, D. Accts. chem. Res. 17, 221–226 (1984).
Grove, D. M. et al. J. Am. chem. Soc. 104, 6609–6616 (1982).
Blomberg, M. R. A., Siegbahn, P. E. M., Nagashima, U. & Wennerberg, J. J. Am. chem. Soc. 113, 424–433 (1991).
Low, J. J. & Goddard, W. A. Organometallics 5, 609–622 (1986).
McMillen, D. F. & Golden, D. M. A. Rev. Phys. Chem. 33, 493–532 (1982).
Jones, W. D. & Feher, F. J. J. Am. chem. Soc. 106, 1650–1663 (1984).
Martinho-Simoes, J. A. & Beauchamp, J. L. Chem. Rev. 90, 629–688 (1990).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Gozin, M., Weisman, A., Ben-David, Y. et al. Activation of a carbon–carbon bond in solution by transition-metal insertion. Nature 364, 699–701 (1993). https://doi.org/10.1038/364699a0
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1038/364699a0
This article is cited by
-
Mn(I)-catalyzed sigmatropic rearrangement of β, γ-unsaturated alcohols
Nature Communications (2023)
-
Dinuclear and tetranuclear group 10 metal complexes constructed from linear tetrasilane comprising both Si-H and Si-Si moieties
Communications Chemistry (2023)
-
C(alkyl)–C(vinyl) bond cleavage enabled by Retro-Pallada-Diels-Alder reaction
Nature Communications (2023)
-
Boron-catalysed hydrogenolysis of unactivated C(aryl)–C(alkyl) bonds
Nature Catalysis (2022)
-
How mono- and diphosphine ligands alter regioselectivity of the Rh-catalyzed annulative cleavage of bicyclo[1.1.0]butanes
Nature Communications (2022)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.