Metathesis of alkanes catalyzed by silica-supported transition metal hydrides

Science

Volumn 276, Issue 5309, 1997, Pages 99-102

  Vidal, Véronique ^a   Théolier, Albert ^a   Thivolle Cazat, Jean ^a   Basset, Jean Marie ^a  

^a UMR 5265   (France)

Author keywords

[No Author keywords available]

Indexed keywords

ALKANE DERIVATIVE; METAL DERIVATIVE; SILICON DIOXIDE;

ARTICLE; CATALYSIS; PRIORITY JOURNAL; REACTION ANALYSIS; THERMODYNAMICS;

EID: 1842367896     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.276.5309.99     Document Type: Article

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18. -1. These values were calculated from data found in D. R. Stull, E. F. Westrum Jr., G. C. Sinke, The Chemical Thermodynamics of Organic Compounds (Krieger, Malabar, FL, 1987).
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20. 500].
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23. -1.
24. -1.
25. -1.
26. -1.
27. In the early stages of the discovery of the olefin metathesis reaction, the most simple mechanism envisaged was a pairwise mechanism in which both olefins would react on the metallic center to give a quasicyclobutane intermediate. This mechanism was later refuted. The simple fact that metathesis of ethane gives methane and propane indicates that the mechanism is nonpairwise, that is, the two alkanes do not play the same role in the mechanism.
28. The oxidative addition of C-C bonds on metallic complexes is a rare process, because it is, in general, thermodynamically disfavored. It has been mainly observed in the case of strained cycles like cyclopropanes, in the course of stoichiometric reactions [R. A. Periana and R. G. Bergman, J. Am. Chem. Soc. 106, 7272 (1984); R. H. Crabtree, Chem. Rev. 85, 245 (1985); R. J. Puddephatt, Coord. Chem. Rev. 33, 149 (1980)]. It has also been observed with an unstrained C-C bond where the resulting formation of a cyclopentadienyl ligand could be the driving force [R. H. Crabtree and R. P. Dion, J. Chem. Soc. Chem. Commun. 1984, 1260 (1984)]. The oxidative addition of strained cycles has also been assumed in the course of catalytic processes involving the insertion of olefins [H. Takaya, T. Suzuki, Y. Kumagai, M. Yamakawa, R. Noyori, J. Org. Chem. 46, 2846 (1981); H. Takaya et al., ibid., p. 2854].
29. The oxidative addition of C-C bonds on metallic complexes is a rare process, because it is, in general, thermodynamically disfavored. It has been mainly observed in the case of strained cycles like cyclopropanes, in the course of stoichiometric reactions [R. A. Periana and R. G. Bergman, J. Am. Chem. Soc. 106, 7272 (1984); R. H. Crabtree, Chem. Rev. 85, 245 (1985); R. J. Puddephatt, Coord. Chem. Rev. 33, 149 (1980)]. It has also been observed with an unstrained C-C bond where the resulting formation of a cyclopentadienyl ligand could be the driving force [R. H. Crabtree and R. P. Dion, J. Chem. Soc. Chem. Commun. 1984, 1260 (1984)]. The oxidative addition of strained cycles has also been assumed in the course of catalytic processes involving the insertion of olefins [H. Takaya, T. Suzuki, Y. Kumagai, M. Yamakawa, R. Noyori, J. Org. Chem. 46, 2846 (1981); H. Takaya et al., ibid., p. 2854].
30. The oxidative addition of C-C bonds on metallic complexes is a rare process, because it is, in general, thermodynamically disfavored. It has been mainly observed in the case of strained cycles like cyclopropanes, in the course of stoichiometric reactions [R. A. Periana and R. G. Bergman, J. Am. Chem. Soc. 106, 7272 (1984); R. H. Crabtree, Chem. Rev. 85, 245 (1985); R. J. Puddephatt, Coord. Chem. Rev. 33, 149 (1980)]. It has also been observed with an unstrained C-C bond where the resulting formation of a cyclopentadienyl ligand could be the driving force [R. H. Crabtree and R. P. Dion, J. Chem. Soc. Chem. Commun. 1984, 1260 (1984)]. The oxidative addition of strained cycles has also been assumed in the course of catalytic processes involving the insertion of olefins [H. Takaya, T. Suzuki, Y. Kumagai, M. Yamakawa, R. Noyori, J. Org. Chem. 46, 2846 (1981); H. Takaya et al., ibid., p. 2854].
31. The oxidative addition of C-C bonds on metallic complexes is a rare process, because it is, in general, thermodynamically disfavored. It has been mainly observed in the case of strained cycles like cyclopropanes, in the course of stoichiometric reactions [R. A. Periana and R. G. Bergman, J. Am. Chem. Soc. 106, 7272 (1984); R. H. Crabtree, Chem. Rev. 85, 245 (1985); R. J. Puddephatt, Coord. Chem. Rev. 33, 149 (1980)]. It has also been observed with an unstrained C-C bond where the resulting formation of a cyclopentadienyl ligand could be the driving force [R. H. Crabtree and R. P. Dion, J. Chem. Soc. Chem. Commun. 1984, 1260 (1984)]. The oxidative addition of strained cycles has also been assumed in the course of catalytic processes involving the insertion of olefins [H. Takaya, T. Suzuki, Y. Kumagai, M. Yamakawa, R. Noyori, J. Org. Chem. 46, 2846 (1981); H. Takaya et al., ibid., p. 2854].
32. The oxidative addition of C-C bonds on metallic complexes is a rare process, because it is, in general, thermodynamically disfavored. It has been mainly observed in the case of strained cycles like cyclopropanes, in the course of stoichiometric reactions [R. A. Periana and R. G. Bergman, J. Am. Chem. Soc. 106, 7272 (1984); R. H. Crabtree, Chem. Rev. 85, 245 (1985); R. J. Puddephatt, Coord. Chem. Rev. 33, 149 (1980)]. It has also been observed with an unstrained C-C bond where the resulting formation of a cyclopentadienyl ligand could be the driving force [R. H. Crabtree and R. P. Dion, J. Chem. Soc. Chem. Commun. 1984, 1260 (1984)]. The oxidative addition of strained cycles has also been assumed in the course of catalytic processes involving the insertion of olefins [H. Takaya, T. Suzuki, Y. Kumagai, M. Yamakawa, R. Noyori, J. Org. Chem. 46, 2846 (1981); H. Takaya et al., ibid., p. 2854].
33. The oxidative addition of C-C bonds on metallic complexes is a rare process, because it is, in general, thermodynamically disfavored. It has been mainly observed in the case of strained cycles like cyclopropanes, in the course of stoichiometric reactions [R. A. Periana and R. G. Bergman, J. Am. Chem. Soc. 106, 7272 (1984); R. H. Crabtree, Chem. Rev. 85, 245 (1985); R. J. Puddephatt, Coord. Chem. Rev. 33, 149 (1980)]. It has also been observed with an unstrained C-C bond where the resulting formation of a cyclopentadienyl ligand could be the driving force [R. H. Crabtree and R. P. Dion, J. Chem. Soc. Chem. Commun. 1984, 1260 (1984)]. The oxidative addition of strained cycles has also been assumed in the course of catalytic processes involving the insertion of olefins [H. Takaya, T. Suzuki, Y. Kumagai, M. Yamakawa, R. Noyori, J. Org. Chem. 46, 2846 (1981); H. Takaya et al., ibid., p. 2854].
34. M. E. Thompson et al., J. Am. Chem. Soc. 109, 203 (1987); P. L. Watson, ibid. 105, 6491 (1983).
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36. H. G. Woo, J. F. Walzer, T. D. Tilley, ibid. 114, 7047 (1992).