Structural dependence of thermodynamics of alkene binding to yttrium alkyl complexes and of kinetics of alkyl migration to coordinated alkenes

Journal of the American Chemical Society

Volumn 125, Issue 9, 2003, Pages 2641-2651

  Casey, Charles P ^a   Tunge, Jon A ^a   Lee, Ting Yu ^a   Fagan, Maureen A ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EPIMERIZATION;

MOLECULAR STRUCTURE; SUBSTITUTION REACTIONS; YTTRIUM COMPOUNDS;

OLEFINS;

ALKENE DERIVATIVE; ALKYL GROUP; METAL; PROPYLENE; YTTRIUM;

ARTICLE; CHEMICAL BINDING; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; EPIMERIZATION; EQUILIBRIUM CONSTANT; LOW TEMPERATURE; MOLECULAR INTERACTION; MOLECULAR STABILITY; THERMODYNAMICS; WARMING;

EID: 0037420349     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0209971     Document Type: Article

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42. For theoretical treatments of agostic interactions in alkene polymerization, see: (a) Prosenc, M. H.; Janiak, C.; Brintzinger, H. H. Organometallics 1992, 11, 4036. (b) Margl, P.; Deng, L.; Ziegler, T. Organometallics 1998, 17, 933. (c) Margl, P.; Deng, L.; Ziegler, T. J. Am. Chem. Soc. 1998, 120, 5517. (d) Wiser, D. C.; Rappe', A. K. Polym. Mater. Sci. Eng. 1996, 74, 423.
43. For theoretical treatments of agostic interactions in alkene polymerization, see: (a) Prosenc, M. H.; Janiak, C.; Brintzinger, H. H. Organometallics 1992, 11, 4036. (b) Margl, P.; Deng, L.; Ziegler, T. Organometallics 1998, 17, 933. (c) Margl, P.; Deng, L.; Ziegler, T. J. Am. Chem. Soc. 1998, 120, 5517. (d) Wiser, D. C.; Rappe', A. K. Polym. Mater. Sci. Eng. 1996, 74, 423.
44. For theoretical treatments of agostic interactions in alkene polymerization, see: (a) Prosenc, M. H.; Janiak, C.; Brintzinger, H. H. Organometallics 1992, 11, 4036. (b) Margl, P.; Deng, L.; Ziegler, T. Organometallics 1998, 17, 933. (c) Margl, P.; Deng, L.; Ziegler, T. J. Am. Chem. Soc. 1998, 120, 5517. (d) Wiser, D. C.; Rappe', A. K. Polym. Mater. Sci. Eng. 1996, 74, 423.
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48. β ≈ 125 Hz for a nonagostic alkyl.
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54. 2.
55. 2 with 3-methyl-1-butene at -50 °C.
56. The α-agostic interaction in TpNbCl(i-Pr)(MeCCMe) is favored by 6.5 eu over the β-agostic interaction: Jaffart, J.; Etienne, M.; Maseras, F.; McGrady, J. E.; Eisenstein, O. J. Am. Chem. Soc. 2001, 123, 6000.
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61. 14 solvent mixture.
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64. The tentative structural assignment of 8 is based on precedent of related reactions. Because the reaction of 6 with propene was used to obtain an upper limit for the rate of propene insertion, rate comparisons do not depend on the accuracy of the structural assignment of 8.
65. In addition to alkene insertion, some decomposition was observed, so the rate constant given represents an upper limit of the rate for propene insertion.
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67. (b) Ystenes, M. Makromol. Chem., Macromol. Symp. 1993, 66, 71.
68. (c) Munoz-Escalona, A.; Ramos, J.; Cruz, V.; Marinez-Salazar, J. J. Polym. Sci., Part A 2000, 38, 571.
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70. 5d
71. 5b
72. -1 and ΔS‡ = -37(8) eu.
73. -1 and 1 eu. respectively.
74. A thorough kinetic analysis shows that the rate of alkene liberation by β-hydride to metal elimination can have an apparent first-order dependence on [alkenel if formation of the secondary alkyl is rate-limiting: Liu, Z.; Somsook, E.; White, C. B.; Rosaaen, K. A.; Landis, C. R. J. Am. Chem. Soc. 2001, 123, 11193.
75. 27
76. We cannot tell the exact reactivity ratio from this experiment because the concentration of propene changes at a different rate than the concentration of 3-methyl-1-butene.
77. The exact coalescence temperature was difficult to discern because substantial quantities of 9 formed by isomerization of 5 prevented proper determination.
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86. Consideration of the geometric requirements for this intramolecular cyclization indicates that only the "front-side" transition state is accessible.
87. Clever catalyst design can inhibit the C-H activation process, making it possible to polymerize propene with yttrocene catalysts: (a) Mitchell, J. P.; Hajela, S.; Brookhart, S. K.; Hardcastle, K. I.; Henling, L. M.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 1045. (b) Coughlin, E. B.; Bercaw, J. E. J. Am. Chem. Soc. 1992, 114, 7606.
88. Clever catalyst design can inhibit the C-H activation process, making it possible to polymerize propene with yttrocene catalysts: (a) Mitchell, J. P.; Hajela, S.; Brookhart, S. K.; Hardcastle, K. I.; Henling, L. M.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 1045. (b) Coughlin, E. B.; Bercaw, J. E. J. Am. Chem. Soc. 1992, 114, 7606.
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