The ansa-effect in permethyltantalocene chemistry: A [Me2Si] ansa bridge promotes olefin-insertion and reductive-elimination reactions for [Me2Si(C5Me4)2]Ta(η2-C2H4)H and [Me2Si(C5Me4)2]TaH3

Chemical Communications

Volumn , Issue 10, 1999, Pages 887-888

  Shin, Jun Ho ^a   Parkin, Gerard ^a  

^a Och Spine at New York Presbyterian Hospitals   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; ETHYLENE; PROTON; SILICONE DERIVATIVE;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHEMISTRY; HYDROGEN BOND;

EID: 0033591276     PISSN: 13597345     EISSN: None     Source Type: Journal    
DOI: 10.1039/a900895k     Document Type: Article

References (30)

1. H. H. Brintzinger, D. Fischer, R. Mülhaupt, B. Rieger and R. M. Waymouth, Angew. Chem., Int. Ed. Engl., 1995, 34, 1143.
2. For leading reports describing differences in the chemistry of ansa and non-ansa systems, see: (a) S. L. J. Conway, T. Dijkstra, L. H. Doerrer, J. C. Green, M. L. H. Green and A. H. H. Stephens, J. Chem. Soc., Dalton Trans., 1998, 2689;
3. (b) H. Lee, P. J. Desrosiers, I. Guzei, A. L. Rheingold and G. Parkin, J. Am. Chem. Soc., 1998, 120, 3255;
4. (c) J. C. Green, Chem. Soc. Rev., 1998, 27, 263.
5. See, for example: (a) G. Parkin, E. Bunel, B. J. Burger, M. S. Trimmer, A. van Asselt and J. E. Bercaw, J. Mol. Catal., 1987, 41, 21; (
6. b) B. J. Burger, B. D. Santarsiero, M. S. Trimmer and J. E. Bercaw, J. Am. Chem. Soc., 1988, 110, 3134;
7. (c) V. C. Gibson, G. Parkin and J. E. Bercaw, Organometallics, 1991, 10, 220.
8. CSD Version 5.16. 3D Search and Research Using the Cambridge Structural Database; F. H. Allen and O. Kennard, Chem. Des. Automat. News, 1993, 8(1), 1, 31-37.
9. CSD Version 5.16. 3D Search and Research Using the Cambridge Structural Database; F. H. Allen and O. Kennard, Chem. Des. Automat. News, 1993, 8(1), 1, 31-37.
10. N. J. Bailey, J. A. Cooper, H. Gailus, M. L. H. Green, J. T. James and M. A. Leech, J. Chem. Soc., Dalton Trans., 1997, 3579.
11. W. A. Herrmann, W. Baratta and E. Herdtweck, J. Organomet. Chem., 1997, 541, 445.
12. c are also known: (a) A. N. Chernega, M. L. H. Green and A. G. Suárez, Can. J. Chem., 1995, 73, 1157;
13. (b) W. A. Herrmann, W. Baratta and E. Herdtweck, Angew. Chem., Int. Ed. Engl., 1996, 35, 1951;
14. (c) P. Chirik and J. E. Bercaw, personal communication.
15. V. C. Gibson, J. E. Bercaw, W. J. Bruton, Jr. and R. D. Sanner, Organometallics, 1986, 5, 976.
16. 3SnCl.
17. -1].
18. L. Labella, A. Chernega and M. L. H. Green, J. Chem. Soc., Dalton Trans., 1995, 395; J. C. Green and C. N. Jardine, J. Chem. Soc., Dalton Trans., 1998, 1057; see also ref. 2(a).
19. L. Labella, A. Chernega and M. L. H. Green, J. Chem. Soc., Dalton Trans., 1995, 395; J. C. Green and C. N. Jardine, J. Chem. Soc., Dalton Trans., 1998, 1057; see also ref. 2(a).
20. J. W. Lauher and R. Hoffmann, J. Am. Chem. Soc., 1976, 98, 1729.
21. V. Varga, J. Hiller, R. Gyepes, M. Polasek, P. Sedmera, U. Thewalt and K. Mach, J. Organomet. Chem., 1997, 538, 63; C. S. Bajgur, W. R. Tikkanen and J. L. Petersen, Inorg. Chem., 1985, 24, 2539.
22. V. Varga, J. Hiller, R. Gyepes, M. Polasek, P. Sedmera, U. Thewalt and K. Mach, J. Organomet. Chem., 1997, 538, 63; C. S. Bajgur, W. R. Tikkanen and J. L. Petersen, Inorg. Chem., 1985, 24, 2539.
23. As has been noted previously, exchange processes of this type do not require the participation of a 16-electron alkyl complexes, but may occur via an 18-electron agostic alkyl species.
24. -1.
25. -1. See ref. 3(b).
26. The term 'inversion' in this sense is being used to refer to ethylene-hydride site (or alkyl-vacancy) interchange. Since the molecule is not chiral, it is not intended to refer to enantiomer interconversion.
27. See, for example: C. P. Casey, M. A. Fagan and S. L. Hallenbeck, Organometallics, 1998, 17, 287 and references therein.
28. cent plane. CCDC 182/1209. See http://www.rsc.org/suppdata/cc/1999/887/ for crystallographic files in .cif format.
29. norm = 148.2°.
30. 3.