Hydrogenolysis of cycloalkanes on a tantalum hydride complex supported on silica and insight into the deactivation pathway by the combined use of 1D solid-state NMR and EXAFS spectroscopies

Chemistry - A European Journal

Volumn 9, Issue 6, 2003, Pages 1426-1434

  Rataboul, Franck ^a   Chabanas, Mathieu ^a   De Mallmann, Aimery ^a   Copéret, Christophe ^a   Thivolle Cazat, Jean ^a   Basset, Jean Marie ^a  

^a UMR 5265   (France)

Author keywords

Alkanes; EXAFS spectroscopy; Hydrogenolysis; NMR spectroscopy; Tantalum

Indexed keywords

CATALYSIS; CHEMICAL BONDS; COMPLEXATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; TANTALUM COMPOUNDS;

HYDROGENOLYSIS;

PARAFFINS;

ALKANE; CARBENE; CYCLOHEPTANE DERIVATIVE; CYCLOPENTANE; SILICON DIOXIDE; TANTALUM;

ABSORPTION SPECTROSCOPY; ARTICLE; CATALYST; CHEMICAL BOND; CHEMICAL MODIFICATION; COMPLEX FORMATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY;

EID: 0037451444     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200390162     Document Type: Article

References (83)

1. For a discussion on mechanistic studies on metal surfaces, see the following papers and references therein: a) F. G. Gault, Adv. Cat. 1981, 30, 1; b) M. Leconte, J. Mol. Catal. 1994, 86, 205; c) F. Locatelli, J.-P. Candy, B. Didillon, G. P. Niccolai, D. Uzio, J.-M. Basset, J. Am. Chem. Soc. 2001, 123, 1658.
2. For a discussion on mechanistic studies on metal surfaces, see the following papers and references therein: a) F. G. Gault, Adv. Cat. 1981, 30, 1; b) M. Leconte, J. Mol. Catal. 1994, 86, 205; c) F. Locatelli, J.-P. Candy, B. Didillon, G. P. Niccolai, D. Uzio, J.-M. Basset, J. Am. Chem. Soc. 2001, 123, 1658.
3. For a discussion on mechanistic studies on metal surfaces, see the following papers and references therein: a) F. G. Gault, Adv. Cat. 1981, 30, 1; b) M. Leconte, J. Mol. Catal. 1994, 86, 205; c) F. Locatelli, J.-P. Candy, B. Didillon, G. P. Niccolai, D. Uzio, J.-M. Basset, J. Am. Chem. Soc. 2001, 123, 1658.
4. C. Copéret, M. Chabanas, R. Petroff Saint-Arroman, J.-M. Basset, Angew. Chem. 2003, 115, 164; Angew. Chem. Int. Ed. 2003, 42, 156.
5. C. Copéret, M. Chabanas, R. Petroff Saint-Arroman, J.-M. Basset, Angew. Chem. 2003, 115, 164; Angew. Chem. Int. Ed. 2003, 42, 156.
6. a) V. Dufaud, G. P. Niccolai, A. Théolier, J. Thivolle-Cazat, J.-M. Basset, J. Am. Chem. Soc. 1995, 117, 4288;
7. b) L. Lefort, V. Dufaud, G. P Niccolai, A. Théolier, J. Thivolle-Cazat, J.-M. Basset, J. Organomet. Chem. 2000, 593-594, 96;
8. c) M. Chabanas, A. E. Quadrelli, C. Copéret, J. Thivolle-Cazat, J.-M. Basset, Angew. Chem. 2001, 113, 4325; Angew. Chem. Int. Ed. 2001, 43, 4493.
9. c) M. Chabanas, A. E. Quadrelli, C. Copéret, J. Thivolle-Cazat, J.-M. Basset, Angew. Chem. 2001, 113, 4325; Angew. Chem. Int. Ed. 2001, 43, 4493.
10. V. Vidal, A. Théolier, J. Thivolle-Cazat, J.-M. Basset, J. Corker J. Am. Chem. Soc. 1996, 118, 4595.
11. V. Vidal, A. Théolier, J. Thivolle-Cazat, J.-M. Basset, J. Chem. Soc. Chem. Commun. 1995, 991.
12. L. Lefort, C. Copéret, M. Taoufik, J. Thivolle-Cazat, J.-M. Basset, Chem. Commun. 2000, 663.
13. a) V. Vidal, A. Théolier, J. Thivolle-Cazat, J.-M. Basset, Science, 1997, 276, 99;
14. b) O. Maury, L. Lefort, V. Vidal, J. Thivolle-Cazat, J.-M. Basset, Angew. Chem. 1999, 111, 2121; Angew. Chem. Int. Ed. 1999, 38, 1952.
15. b) O. Maury, L. Lefort, V. Vidal, J. Thivolle-Cazat, J.-M. Basset, Angew. Chem. 1999, 111, 2121; Angew. Chem. Int. Ed. 1999, 38, 1952.
16. M. Chabanas, V. Vidal, C. Copéret, J. Thivolle-Cazat, J.-M. Basset, Angew. Chem. 2000, 112, 2038; Angew. Chem. Int. Ed. 2000, 39, 1962.
17. M. Chabanas, V. Vidal, C. Copéret, J. Thivolle-Cazat, J.-M. Basset, Angew. Chem. 2000, 112, 2038; Angew. Chem. Int. Ed. 2000, 39, 1962.
18. 3Ti-H: C. Rozier, G. P. Niccolai, J.-M. Basset, J. Am. Chem. Soc. 1997, 119, 848.
19. 3Ti-H: C. Rozier, G. P. Niccolai, J.-M. Basset, J. Am. Chem. Soc. 1997, 119, 848.
20. 3Ti-H: C. Rozier, G. P. Niccolai, J.-M. Basset, J. Am. Chem. Soc. 1997, 119, 848.
21. 3Ti-H: C. Rozier, G. P. Niccolai, J.-M. Basset, J. Am. Chem. Soc. 1997, 119, 848.
22. 3Ti-H: C. Rozier, G. P. Niccolai, J.-M. Basset, J. Am. Chem. Soc. 1997, 119, 848.
23. 3Ti-H: C. Rozier, G. P. Niccolai, J.-M. Basset, J. Am. Chem. Soc. 1997, 119, 848.
24. 3Ti-H: C. Rozier, G. P. Niccolai, J.-M. Basset, J. Am. Chem. Soc. 1997, 119, 848.
25. b) β-Alkyl transfer has been proposed to explain the differences in the hydrogenolysis of cycloalkanes in dependence on the ring size on silica-supported Group 4 complexes: G. P. Niccolai, J.-M. Basset in Catalytic Activation and Functionalisation of Light Alkanes (Eds.: E. R. Derouane, J. Haber, F. Lemos, F. Ramôa Ribeiro, M. Guismet), Nato ASI Series, Kluwer Academic Press, Dordrecht, 1998, p. 111; S. Reyes, G. P. Niccolai, J.-M. Basset, unpublished results.
26. b) β-Alkyl transfer has been proposed to explain the differences in the hydrogenolysis of cycloalkanes in dependence on the ring size on silica-supported Group 4 complexes: G. P. Niccolai, J.-M. Basset in Catalytic Activation and Functionalisation of Light Alkanes (Eds.: E. R. Derouane, J. Haber, F. Lemos, F. Ramôa Ribeiro, M. Guismet), Nato ASI Series, Kluwer Academic Press, Dordrecht, 1998, p. 111; S. Reyes, G. P. Niccolai, J.-M. Basset, unpublished results.
27. For a theoretical study on the hydrogenolysis of alkane with zirconium hydride, see J. J. Mortensen, M. Parrinello, J. Phys. Chem. B 2000, 104, 2901.
28. Taken in part from the master degree of M. Chabanas, Université Claude Bernard, 1998. Presented at SFC-2000, 18-22 September 2000, Rennes (France).
29. Isomerisation refers to a process in which a cyclic alkane is transformed into another cyclic product containing the same number of carbon atoms (e.g., methylcyclohexane and cycloheptane), while contraction refers to a process which transforms a cycloalkane into a cycloalkane having a different total number of carbon atoms (e.g., cyclohexane and cycloheptane).
30. 2 Ta complexes, see: a) R. E. Lapointe, P. T. Wolczanski, J. F. Mitchell, J. Am. Chem. Soc. 1986, 108, 6382; b) K. R. Ballard, I. M. Gardiner, D. E. Wigley, J. Am. Chem. Soc. 1989, 111, 2159; c) D. H. Berry, T. D. Tilley, J. Am. Chem. Soc. 1989, 111, 8049. d) T. Y. Meyer, L. Messerle, J. Am. Chem. Soc. 1990, 112, 4564; f) J. B. Bonanno, T. P. Henry, D. R. Neithamer, P. T. Wolczanski, E. B. Lobkovsky, J. Am. Chem. Soc. 1996, 118, 5132.
31. 2 Ta complexes, see: a) R. E. Lapointe, P. T. Wolczanski, J. F. Mitchell, J. Am. Chem. Soc. 1986, 108, 6382; b) K. R. Ballard, I. M. Gardiner, D. E. Wigley, J. Am. Chem. Soc. 1989, 111, 2159; c) D. H. Berry, T. D. Tilley, J. Am. Chem. Soc. 1989, 111, 8049. d) T. Y. Meyer, L. Messerle, J. Am. Chem. Soc. 1990, 112, 4564; f) J. B. Bonanno, T. P. Henry, D. R. Neithamer, P. T. Wolczanski, E. B. Lobkovsky, J. Am. Chem. Soc. 1996, 118, 5132.
32. 2 Ta complexes, see: a) R. E. Lapointe, P. T. Wolczanski, J. F. Mitchell, J. Am. Chem. Soc. 1986, 108, 6382; b) K. R. Ballard, I. M. Gardiner, D. E. Wigley, J. Am. Chem. Soc. 1989, 111, 2159; c) D. H. Berry, T. D. Tilley, J. Am. Chem. Soc. 1989, 111, 8049. d) T. Y. Meyer, L. Messerle, J. Am. Chem. Soc. 1990, 112, 4564; f) J. B. Bonanno, T. P. Henry, D. R. Neithamer, P. T. Wolczanski, E. B. Lobkovsky, J. Am. Chem. Soc. 1996, 118, 5132.
33. 2 Ta complexes, see: a) R. E. Lapointe, P. T. Wolczanski, J. F. Mitchell, J. Am. Chem. Soc. 1986, 108, 6382; b) K. R. Ballard, I. M. Gardiner, D. E. Wigley, J. Am. Chem. Soc. 1989, 111, 2159; c) D. H. Berry, T. D. Tilley, J. Am. Chem. Soc. 1989, 111, 8049. d) T. Y. Meyer, L. Messerle, J. Am. Chem. Soc. 1990, 112, 4564; f) J. B. Bonanno, T. P. Henry, D. R. Neithamer, P. T. Wolczanski, E. B. Lobkovsky, J. Am. Chem. Soc. 1996, 118, 5132.
34. 2 Ta complexes, see: a) R. E. Lapointe, P. T. Wolczanski, J. F. Mitchell, J. Am. Chem. Soc. 1986, 108, 6382; b) K. R. Ballard, I. M. Gardiner, D. E. Wigley, J. Am. Chem. Soc. 1989, 111, 2159; c) D. H. Berry, T. D. Tilley, J. Am. Chem. Soc. 1989, 111, 8049. d) T. Y. Meyer, L. Messerle, J. Am. Chem. Soc. 1990, 112, 4564; f) J. B. Bonanno, T. P. Henry, D. R. Neithamer, P. T. Wolczanski, E. B. Lobkovsky, J. Am. Chem. Soc. 1996, 118, 5132.
35. a) J. R. Lisko, W. M. Jones, Organometallics 1985, 4, 944;
36. b) Y. Stenstrøm; W. M. Jones, Organometallics 1986, 5, 178;
37. c) The reverse step has been exemplified many times (see ref. [15]), and the relative energies discussed: H. Berke, R. Hoffmann, J. Am. Chem. Soc. 1978, 100, 7224.
38. For examples of the reverse step (de-insertion), see: a) P. R. Sharp, R. R. Schrock, J. Organometallic. Chem. 1979, 171, 43; b) J. C. Hayes, G. D. N. Pearson, N. J. Cooper, J. Am. Chem. Soc. 1981, 103, 4648; c) D. L. Thorn, T. H. Tulip, J. Am. Chem. Soc. 1981, 103, 5984; d) H. Kletzin, H. Werner, O. Serhadli, M. L. Ziegler, Angew. Chem. 1983, 95, 49; Angew. Chem. Int. Ed. 1983, 22, 46; e) P. Jernakoff, N. J. Cooper, J. Am. Chem. Soc. 1984, 106, 3026; f) G. Parkin, E. Bunel, M. S. Trimmer, A. van Asselt, J. E. Bercaw, J. Mol. Catal. 1987, 47,21.
39. For examples of the reverse step (de-insertion), see: a) P. R. Sharp, R. R. Schrock, J. Organometallic. Chem. 1979, 171, 43; b) J. C. Hayes, G. D. N. Pearson, N. J. Cooper, J. Am. Chem. Soc. 1981, 103, 4648; c) D. L. Thorn, T. H. Tulip, J. Am. Chem. Soc. 1981, 103, 5984; d) H. Kletzin, H. Werner, O. Serhadli, M. L. Ziegler, Angew. Chem. 1983, 95, 49; Angew. Chem. Int. Ed. 1983, 22, 46; e) P. Jernakoff, N. J. Cooper, J. Am. Chem. Soc. 1984, 106, 3026; f) G. Parkin, E. Bunel, M. S. Trimmer, A. van Asselt, J. E. Bercaw, J. Mol. Catal. 1987, 47,21.
40. For examples of the reverse step (de-insertion), see: a) P. R. Sharp, R. R. Schrock, J. Organometallic. Chem. 1979, 171, 43; b) J. C. Hayes, G. D. N. Pearson, N. J. Cooper, J. Am. Chem. Soc. 1981, 103, 4648; c) D. L. Thorn, T. H. Tulip, J. Am. Chem. Soc. 1981, 103, 5984; d) H. Kletzin, H. Werner, O. Serhadli, M. L. Ziegler, Angew. Chem. 1983, 95, 49; Angew. Chem. Int. Ed. 1983, 22, 46; e) P. Jernakoff, N. J. Cooper, J. Am. Chem. Soc. 1984, 106, 3026; f) G. Parkin, E. Bunel, M. S. Trimmer, A. van Asselt, J. E. Bercaw, J. Mol. Catal. 1987, 47,21.
41. For examples of the reverse step (de-insertion), see: a) P. R. Sharp, R. R. Schrock, J. Organometallic. Chem. 1979, 171, 43; b) J. C. Hayes, G. D. N. Pearson, N. J. Cooper, J. Am. Chem. Soc. 1981, 103, 4648; c) D. L. Thorn, T. H. Tulip, J. Am. Chem. Soc. 1981, 103, 5984; d) H. Kletzin, H. Werner, O. Serhadli, M. L. Ziegler, Angew. Chem. 1983, 95, 49; Angew. Chem. Int. Ed. 1983, 22, 46; e) P. Jernakoff, N. J. Cooper, J. Am. Chem. Soc. 1984, 106, 3026; f) G. Parkin, E. Bunel, M. S. Trimmer, A. van Asselt, J. E. Bercaw, J. Mol. Catal. 1987, 47,21.
42. For examples of the reverse step (de-insertion), see: a) P. R. Sharp, R. R. Schrock, J. Organometallic. Chem. 1979, 171, 43; b) J. C. Hayes, G. D. N. Pearson, N. J. Cooper, J. Am. Chem. Soc. 1981, 103, 4648; c) D. L. Thorn, T. H. Tulip, J. Am. Chem. Soc. 1981, 103, 5984; d) H. Kletzin, H. Werner, O. Serhadli, M. L. Ziegler, Angew. Chem. 1983, 95, 49; Angew. Chem. Int. Ed. 1983, 22, 46; e) P. Jernakoff, N. J. Cooper, J. Am. Chem. Soc. 1984, 106, 3026; f) G. Parkin, E. Bunel, M. S. Trimmer, A. van Asselt, J. E. Bercaw, J. Mol. Catal. 1987, 47,21.
43. For examples of the reverse step (de-insertion), see: a) P. R. Sharp, R. R. Schrock, J. Organometallic. Chem. 1979, 171, 43; b) J. C. Hayes, G. D. N. Pearson, N. J. Cooper, J. Am. Chem. Soc. 1981, 103, 4648; c) D. L. Thorn, T. H. Tulip, J. Am. Chem. Soc. 1981, 103, 5984; d) H. Kletzin, H. Werner, O. Serhadli, M. L. Ziegler, Angew. Chem. 1983, 95, 49; Angew. Chem. Int. Ed. 1983, 22, 46; e) P. Jernakoff, N. J. Cooper, J. Am. Chem. Soc. 1984, 106, 3026; f) G. Parkin, E. Bunel, M. S. Trimmer, A. van Asselt, J. E. Bercaw, J. Mol. Catal. 1987, 47,21.
44. For examples of the reverse step (de-insertion), see: a) P. R. Sharp, R. R. Schrock, J. Organometallic. Chem. 1979, 171, 43; b) J. C. Hayes, G. D. N. Pearson, N. J. Cooper, J. Am. Chem. Soc. 1981, 103, 4648; c) D. L. Thorn, T. H. Tulip, J. Am. Chem. Soc. 1981, 103, 5984; d) H. Kletzin, H. Werner, O. Serhadli, M. L. Ziegler, Angew. Chem. 1983, 95, 49; Angew. Chem. Int. Ed. 1983, 22, 46; e) P. Jernakoff, N. J. Cooper, J. Am. Chem. Soc. 1984, 106, 3026; f) G. Parkin, E. Bunel, M. S. Trimmer, A. van Asselt, J. E. Bercaw, J. Mol. Catal. 1987, 47,21.
45. For some examples of σ-bond metathesis mechanism with molecular organometallics, see: a) P. L. Watson, J. Am. Chem. Soc. 1983, 105, 6491; b) P. L. Watson G. W. Parshall, Acc. Chem. Res. 1985, 18, 51; c) M. E. Thompson, S. M. Baxter, A. R. Bulls, B. J. Burger, M. C. Nolan, B. D. Santarsiero, W. P. Schaefer, J. E. Bercaw, J. Am. Chem. Soc. 1987, 109, 203; d) H.-G. Woo, J. F. Walzer, T. D. Tilley, J. Am. Chem. Soc. 1992, 114, 7047.
46. For some examples of σ-bond metathesis mechanism with molecular organometallics, see: a) P. L. Watson, J. Am. Chem. Soc. 1983, 105, 6491; b) P. L. Watson G. W. Parshall, Acc. Chem. Res. 1985, 18, 51; c) M. E. Thompson, S. M. Baxter, A. R. Bulls, B. J. Burger, M. C. Nolan, B. D. Santarsiero, W. P. Schaefer, J. E. Bercaw, J. Am. Chem. Soc. 1987, 109, 203; d) H.-G. Woo, J. F. Walzer, T. D. Tilley, J. Am. Chem. Soc. 1992, 114, 7047.
47. For some examples of σ-bond metathesis mechanism with molecular organometallics, see: a) P. L. Watson, J. Am. Chem. Soc. 1983, 105, 6491; b) P. L. Watson G. W. Parshall, Acc. Chem. Res. 1985, 18, 51; c) M. E. Thompson, S. M. Baxter, A. R. Bulls, B. J. Burger, M. C. Nolan, B. D. Santarsiero, W. P. Schaefer, J. E. Bercaw, J. Am. Chem. Soc. 1987, 109, 203; d) H.-G. Woo, J. F. Walzer, T. D. Tilley, J. Am. Chem. Soc. 1992, 114, 7047.
48. For some examples of σ-bond metathesis mechanism with molecular organometallics, see: a) P. L. Watson, J. Am. Chem. Soc. 1983, 105, 6491; b) P. L. Watson G. W. Parshall, Acc. Chem. Res. 1985, 18, 51; c) M. E. Thompson, S. M. Baxter, A. R. Bulls, B. J. Burger, M. C. Nolan, B. D. Santarsiero, W. P. Schaefer, J. E. Bercaw, J. Am. Chem. Soc. 1987, 109, 203; d) H.-G. Woo, J. F. Walzer, T. D. Tilley, J. Am. Chem. Soc. 1992, 114, 7047.
49. B. Rybtchinski, D. Milstein, Angew. Chem. 1999, 111, 918; Angew. Chem. Int. Ed. 1999, 38, 871.
50. B. Rybtchinski, D. Milstein, Angew. Chem. 1999, 111, 918; Angew. Chem. Int. Ed. 1999, 38, 871.
51. For some examples of γ-abstraction with early transition metals or lanthanides, see: a) P. R. Sharp, D. Astruc, R. R. Schrock, J. Organometal. Chem. 1979, 182, 477; b) C. M. Fendrick, T. J. Marks, J. Am. Chem. Soc. 1984, 106, 2214; c) C. M. Fendrick, T. J. Marks, J. Am. Chem. Soc. 1986, 108, 425; d) J. W. Bruno, T. J. Marks, L. R. Moss, J. Am. Chem. Soc. 1983, 105, 6824; e) J. Cheon, D. M. Rogers, G. S. Girolami, J. Am. Chem. Soc. 1997, 119, 6804.
52. For some examples of γ-abstraction with early transition metals or lanthanides, see: a) P. R. Sharp, D. Astruc, R. R. Schrock, J. Organometal. Chem. 1979, 182, 477; b) C. M. Fendrick, T. J. Marks, J. Am. Chem. Soc. 1984, 106, 2214; c) C. M. Fendrick, T. J. Marks, J. Am. Chem. Soc. 1986, 108, 425; d) J. W. Bruno, T. J. Marks, L. R. Moss, J. Am. Chem. Soc. 1983, 105, 6824; e) J. Cheon, D. M. Rogers, G. S. Girolami, J. Am. Chem. Soc. 1997, 119, 6804.
53. For some examples of γ-abstraction with early transition metals or lanthanides, see: a) P. R. Sharp, D. Astruc, R. R. Schrock, J. Organometal. Chem. 1979, 182, 477; b) C. M. Fendrick, T. J. Marks, J. Am. Chem. Soc. 1984, 106, 2214; c) C. M. Fendrick, T. J. Marks, J. Am. Chem. Soc. 1986, 108, 425; d) J. W. Bruno, T. J. Marks, L. R. Moss, J. Am. Chem. Soc. 1983, 105, 6824; e) J. Cheon, D. M. Rogers, G. S. Girolami, J. Am. Chem. Soc. 1997, 119, 6804.
54. For some examples of γ-abstraction with early transition metals or lanthanides, see: a) P. R. Sharp, D. Astruc, R. R. Schrock, J. Organometal. Chem. 1979, 182, 477; b) C. M. Fendrick, T. J. Marks, J. Am. Chem. Soc. 1984, 106, 2214; c) C. M. Fendrick, T. J. Marks, J. Am. Chem. Soc. 1986, 108, 425; d) J. W. Bruno, T. J. Marks, L. R. Moss, J. Am. Chem. Soc. 1983, 105, 6824; e) J. Cheon, D. M. Rogers, G. S. Girolami, J. Am. Chem. Soc. 1997, 119, 6804.
55. For some examples of γ-abstraction with early transition metals or lanthanides, see: a) P. R. Sharp, D. Astruc, R. R. Schrock, J. Organometal. Chem. 1979, 182, 477; b) C. M. Fendrick, T. J. Marks, J. Am. Chem. Soc. 1984, 106, 2214; c) C. M. Fendrick, T. J. Marks, J. Am. Chem. Soc. 1986, 108, 425; d) J. W. Bruno, T. J. Marks, L. R. Moss, J. Am. Chem. Soc. 1983, 105, 6824; e) J. Cheon, D. M. Rogers, G. S. Girolami, J. Am. Chem. Soc. 1997, 119, 6804.
56. a) H. W. Turner, R. R. Schrock, J. Am. Chem. Soc. 1982, 104, 2331;
57. b) S. J. Holmes, D. N. Clark, H. W. Turner, R. R. Schrock, J. Am. Chem. Soc. 1982, 104, 6322;
58. c) A. van Asselt, B. J. Burger, V. C. Gibson, J. E. Bercaw, J. Am. Chem. Soc. 1986, 108, 5347;
59. d) G. Parkin, E. Bunel, M. S. Trimmer, A. van Asselt, J. E. Bercaw, J. Mol. Cat. 1987, 41, 21;
60. e) R. R. Schrock, K.-Y. Shih, D. A. Dobbs, W. M. Davies, J. Am. Chem. Soc. 1995, 117, 6609.
61. a) S. M. Rocklage, J. D. Fellmann, G. A. Rupprecht, L. W. Messerle, R. R. Schrock, J. Am. Chem. Soc. 1981, 103, 1440;
62. b) K. C. Wallace, J. C. Dewan, R. R. Schrock, Organometallics 1986, 5, 2162;
63. c) K. C. Wallace, A. H. Liu, J. C. Dewan, R. R. Schrock, J. Am. Chem. Soc. 1988, 110, 4964.
64. Olefin Metathesis and Metathesis Polymerization (Eds.: K. J. Ivin, J. C. Mol), Academic Press, San Diego, 1997.
65. The reverse step has been exemplified: C. Andes, S. B. Harkins, S. Murtuza, K. Oyler, A. Sen, J. Am. Chem. Soc. 2001, 123, 7423.
66. For some examples of β-alkyl transfer with early transition metals or lanthanides, see: a) P. L. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) P. L. Watson, G. W. Parshall, Acc. Chem. Res. 1985, 18, 51; c) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; d) L. Schock, T. Marks, J. Am. Chem. Soc. 1990, 110, 7701; e) B. Burger, M. Thompson, D. Cotter, J. Bercaw, J. Am. Chem. Soc. 1990, 112, 1566; f) K. McNeill, R. A. Andersen, R. G. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; g) A. D. Horton, Organometallics 1996, 15, 2675; h) M. Etienne, R. Mathieu, B. Donnadieu, J. Am. Chem. Soc. 1997, 119, 3218.
67. For some examples of β-alkyl transfer with early transition metals or lanthanides, see: a) P. L. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) P. L. Watson, G. W. Parshall, Acc. Chem. Res. 1985, 18, 51; c) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; d) L. Schock, T. Marks, J. Am. Chem. Soc. 1990, 110, 7701; e) B. Burger, M. Thompson, D. Cotter, J. Bercaw, J. Am. Chem. Soc. 1990, 112, 1566; f) K. McNeill, R. A. Andersen, R. G. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; g) A. D. Horton, Organometallics 1996, 15, 2675; h) M. Etienne, R. Mathieu, B. Donnadieu, J. Am. Chem. Soc. 1997, 119, 3218.
68. For some examples of β-alkyl transfer with early transition metals or lanthanides, see: a) P. L. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) P. L. Watson, G. W. Parshall, Acc. Chem. Res. 1985, 18, 51; c) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; d) L. Schock, T. Marks, J. Am. Chem. Soc. 1990, 110, 7701; e) B. Burger, M. Thompson, D. Cotter, J. Bercaw, J. Am. Chem. Soc. 1990, 112, 1566; f) K. McNeill, R. A. Andersen, R. G. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; g) A. D. Horton, Organometallics 1996, 15, 2675; h) M. Etienne, R. Mathieu, B. Donnadieu, J. Am. Chem. Soc. 1997, 119, 3218.
69. For some examples of β-alkyl transfer with early transition metals or lanthanides, see: a) P. L. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) P. L. Watson, G. W. Parshall, Acc. Chem. Res. 1985, 18, 51; c) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; d) L. Schock, T. Marks, J. Am. Chem. Soc. 1990, 110, 7701; e) B. Burger, M. Thompson, D. Cotter, J. Bercaw, J. Am. Chem. Soc. 1990, 112, 1566; f) K. McNeill, R. A. Andersen, R. G. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; g) A. D. Horton, Organometallics 1996, 15, 2675; h) M. Etienne, R. Mathieu, B. Donnadieu, J. Am. Chem. Soc. 1997, 119, 3218.
70. For some examples of β-alkyl transfer with early transition metals or lanthanides, see: a) P. L. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) P. L. Watson, G. W. Parshall, Acc. Chem. Res. 1985, 18, 51; c) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; d) L. Schock, T. Marks, J. Am. Chem. Soc. 1990, 110, 7701; e) B. Burger, M. Thompson, D. Cotter, J. Bercaw, J. Am. Chem. Soc. 1990, 112, 1566; f) K. McNeill, R. A. Andersen, R. G. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; g) A. D. Horton, Organometallics 1996, 15, 2675; h) M. Etienne, R. Mathieu, B. Donnadieu, J. Am. Chem. Soc. 1997, 119, 3218.
71. For some examples of β-alkyl transfer with early transition metals or lanthanides, see: a) P. L. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) P. L. Watson, G. W. Parshall, Acc. Chem. Res. 1985, 18, 51; c) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; d) L. Schock, T. Marks, J. Am. Chem. Soc. 1990, 110, 7701; e) B. Burger, M. Thompson, D. Cotter, J. Bercaw, J. Am. Chem. Soc. 1990, 112, 1566; f) K. McNeill, R. A. Andersen, R. G. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; g) A. D. Horton, Organometallics 1996, 15, 2675; h) M. Etienne, R. Mathieu, B. Donnadieu, J. Am. Chem. Soc. 1997, 119, 3218.
72. For some examples of β-alkyl transfer with early transition metals or lanthanides, see: a) P. L. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) P. L. Watson, G. W. Parshall, Acc. Chem. Res. 1985, 18, 51; c) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; d) L. Schock, T. Marks, J. Am. Chem. Soc. 1990, 110, 7701; e) B. Burger, M. Thompson, D. Cotter, J. Bercaw, J. Am. Chem. Soc. 1990, 112, 1566; f) K. McNeill, R. A. Andersen, R. G. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; g) A. D. Horton, Organometallics 1996, 15, 2675; h) M. Etienne, R. Mathieu, B. Donnadieu, J. Am. Chem. Soc. 1997, 119, 3218.
73. For some examples of β-alkyl transfer with early transition metals or lanthanides, see: a) P. L. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) P. L. Watson, G. W. Parshall, Acc. Chem. Res. 1985, 18, 51; c) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; d) L. Schock, T. Marks, J. Am. Chem. Soc. 1990, 110, 7701; e) B. Burger, M. Thompson, D. Cotter, J. Bercaw, J. Am. Chem. Soc. 1990, 112, 1566; f) K. McNeill, R. A. Andersen, R. G. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; g) A. D. Horton, Organometallics 1996, 15, 2675; h) M. Etienne, R. Mathieu, B. Donnadieu, J. Am. Chem. Soc. 1997, 119, 3218.
74. 5 compounds, is underestimated in this experiment, since only the gas phase was monitored.
75. For an example of a molecular cyclopentyltantalum complex for which the ipso-carbon chemical shift has been reported (δ = 112.6 ppm), see: S. W. Schweiger, M. M. Salberg, A. L. Pulvirenti, E. E. Freeman, P. E. Fanwick, I. P. Rothwell, J. Chem. Soc. Dalton Trans. 2001, 2020.
76. For an example of transformation of a rhenium hydrido complex into cyclopentadienyl complex by activation of cyclopentane, see: D. Baudry, M. Ephritikhine, H. Felkin, J. Chem. Soc. Chem. Commun. 1980, 24, 1243.
77. The bond lengths found fall in the classical range observed for similar compounds: a) A. G. Orpen, L. Brammer, F. H. Allen, O. Kennard, D. G. Watson, R. Taylor, J. Chem. Soc. Dalton Trans. 1989, 12, S1; b) F. H. Allen, O. Kennard, Chem. Design Automation News, 1993, 8, 1, 31-37.
78. The bond lengths found fall in the classical range observed for similar compounds: a) A. G. Orpen, L. Brammer, F. H. Allen, O. Kennard, D. G. Watson, R. Taylor, J. Chem. Soc. Dalton Trans. 1989, 12, S1; b) F. H. Allen, O. Kennard, Chem. Design Automation News, 1993, 8, 1, 31-37.
79. 2}] (O, I, Guzyr, M. Schormann, J. Schimkowiak, H. W. Roesky, C. Lehmann, M. G. Walawalkar, G. Mrilani, H. Murugavel, H.-G. Schmidt, M. Noltemeyer, Organometallics 1999, 18, 832).
80. 2}] (O, I, Guzyr, M. Schormann, J. Schimkowiak, H. W. Roesky, C. Lehmann, M. G. Walawalkar, G. Mrilani, H. Murugavel, H.-G. Schmidt, M. Noltemeyer, Organometallics 1999, 18, 832).
81. A. Michalowicz, "Logiciels pour la chimie", Ed. Société Française de Chimie, Paris 1991, p. 102.
82. B. Lengeler, P. Eisenberger, Phys. Rev. B 1980, 21, 4507.
83. S. I. Zabinsky, J. J. Rehr, A, Ankudinov, R. C. Albers, M. Eller, J. Phys. Rev. B 1995, 26, 148.