The ansa-effect in zirconocene chemistry: The syntheses and interconversions of the hydride complexes {[Me2Si(C 5Me4)2]Zr(H)(μ-H)}2, [Me 2SiC5Me4O2]ZrH2(PMe 3), and [Me2Si(C5Me4) 2]Zr(Ph)H

Journal of the American Chemical Society

Volumn 120, Issue 13, 1998, Pages 3255-3256

  Lee, Hyosun ^a   Desrosiers, Peter J ^a,c   Guzei, Ilia ^b   Rheingold, Arnold L ^b   Parkin, Gerard ^a  

^a Columbia University ^*  (United States)

^b UNIVERSITY OF DELAWARE   (United States)

^c UNIVERSITY OF THE VIRGIN ISLANDS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001660449     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja9742242     Document Type: Letter

References (46)

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8. The term ansa (meaning bent handle, attached at both ends) was first introduced with respect to metallocene chemistry by Brintzinger.
9. See: Smith, J. A.; von Seyerl, J.; Huttner, G.; Brintzinger, H. H. J. Organomet. Chem. 1979, 173, 175-185.
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15. 2] ansa ligand to lanthanide chemistry, with the intention that the ansa bridge would create a more "open" coordination sphere.
16. See: Fendrick, C. M.; Schertz, L. D.; Day, V. W.; Marks, T. J. Organometallics 1988, 7, 1828-1838 and references therein.
17. Wolczanski, P. T.; Bercaw, J. E. Organometallics 1982, 1, 193-199.
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21. 1 = 0.0473 [I < 2σ(I)].
22. For example, the Zr-C-C bond angles [98.5(4)° and 146.0(5)°] deviate considerably from 120°.
23. 2.
24. 2][PhH].
25. Manriquez, J. M.; McAlister, D. R.; Sanner, R. D.; Bercaw, J. E. J. Am. Chem. Soc. 1978, 100, 2716-2724.
26. l4c (a) Jones, S. B.; Petersen, J. L. Inorg. Chem. 1981, 20, 2889-2894.
27. (b) Choukroun, R.; Dahan, F.; Larsonneur, A.M.; Samuel, E.; Petersen, J.; Meunier, P.; Somay, C. Organometallics 1991, 10, 374-376.
28. (c) Larsonneur, A.-M.; Choukroun, R; Jaud, J. Organometallics 1993, 12, 3216-3224.
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30. (b) den Haan, K. H.; Wielstra, Y.; Teuben, J. H. Organometallics 1987, 6, 2053-2060.
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32. x) (x = 0-3) exhibits four hydride signals attributable to four isotopomers (δ 3.39, 3.44, 3.48, and 3.53 at 200 K), a result that is only consistent with a dimeric structure persisting under these conditions.
33. 1H-Me) NMR spectrum at room temperature, thereby confirming the presence of two hydride ligands.
34. 1H-Me) NMR spectrum at -70°C
35. -1, ΔS± = 10(1) eu.
36. 15 In contrast, the hydride signal for the ansa analogue only varies from δ 4.02 to 4.17 ppm over the same temperature range.
37. 1 relaxation studies. See Supporting Information.
38. Manriquez, J. M.; McAlister, D. R.; Sanner, R. D.; Bercaw, J. E. J. Am. Chem. Soc. 1976, 98, 6733-6735.
39. (a) Bajgur, C. S.; Tikkanen, W. R.; Petersen, J. L. Inorg. Chem. 1985, 24, 2539-2546.
40. (b) Siedle, A. R.; Newmark, R. A.; Lamanna, W. M.; Schroepfer, J. N. Polyhedron 1990, 9, 301-308.
41. (c) Ryan, M. F.; Siedle, A. R.; Burk, M. J.; Richardson, D. E. Organometallics 1992, 11, 4231-4237.
42. Gassman, P. G.; Deck, P. A.; Winter, C. H.; Dobbs, D. A.; Cao, D. H. Organometallics 1992, 11, 959-960.
43. 2Si] ansa system, see: Woo, T. K.; Fan, L.; Ziegler, T. Organometallics 1994, 13, 2252-2261.
44. 2, the Zr-C bond lengths range from 2.52 to 2.54 Å. Lee, H.; Parkin, G. Unpublished results.
45. Bailey, N. J.; Green, M. L. H.; Leech, M. A.; Saunders: J. F.; Tidswell, H. M. J. Organomet. Chem. 1997, 538, 111-118.
46. x, (x = 1, 2). See ref 4b.