Ligand mobility and solution structures of the metallocenium ion pairs [Me2C(Cp)(fluorenyl)MCH2SiMe3+ -X-] (M = Zr, Hf; X = MeB(C6F5)3, B(C6F5)4)

Organometallics

Volumn 27, Issue 21, 2008, Pages 5474-5487

  Alonso Moreno, Carlos ^a,d   Lancaster, Simon J ^a   Wright, Joseph A ^a   Hughes, David L ^a   Zuccaccia, Cristiano ^b   Correa, Andrea ^c   Macchioni, Alceo ^b   Cavallo, Luigi ^c   Bochmann, Manfred ^a  

^a UNIVERSITY OF EAST ANGLIA   (United Kingdom)

^b UNIVERSITY OF PERUGIA   (Italy)

^c UNIVERSITY OF SALERNO   (Italy)

^d UNIVERSITY OF CASTILLA LA MANCHA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

AGGLOMERATION; CONCENTRATION (PROCESS); DYNAMICS; FLOW INTERACTIONS; HAFNIUM; LIGANDS; MOLECULAR DYNAMICS; NUCLEAR MAGNETIC RESONANCE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; ORGANOMETALLICS; QUANTUM CHEMISTRY; RATE CONSTANTS; REACTION KINETICS; SILICON; TOLUENE; ZIRCONIUM;

AGOSTIC INTERACTIONS; ALKYL METALLOCENE COMPLEXES; CATALYTIC ACTIVITIES; EPIMERIZATION; EXCHANGE RATES; FIELD GRADIENTS; FLUORENYL; ION AGGREGATES; ION CONCENTRATIONS; ION PAIRS; LIGAND MOBILITIES; METALLOCENIUM IONS; MILLIMOLAR CONCENTRATIONS; MOLECULAR DYNAMICS CALCULATIONS; NMR MEASUREMENTS; NMR SPECTROSCOPIES; SOLUTION STRUCTURES; X-RAY DIFFRACTIONS;

IONS;

EID: 56049119840     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om800486p     Document Type: Article

References (99)

1. Reviews: (a) Bochmann, M. J. Organomet. Chem. 2004, 689, 3982.
2. (b) Erker, G. Acc. Chem, Res. 2001, 34, 309.
3. (c) Chen, E. Y.-X.; Marks, T. J. Chem. Rev. 2000, 100, 1391.
4. (d) Resconi, L.; Cavallo, L.; Fait, A.; Piemontesi, F. Chem. Rev. 2000, 100, 1253.
5. (e) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255.
6. (f) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143.
7. (g) Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325.
8. (a) Song, F.; Cannon, R. D.; Bochmann, M. J. Am. Chem. Soc. 2003, 125, 7641.
9. (b) Song, F.; Hannant, M. D.; Cannon, R. D.; Bochmann, M. Macromol. Symp. 2004, 213, 173.
10. (c) Bochmann, M.; Song, F.; Rodriguez, A.; Cannon, R. D. PMSE Prepr. 2002, 87, 36.
11. (d) Rodriguez-Delgado, A.; Hannant, M. D.; Lancaster, S. J.; Bochmann, M. Macromol. Chem. Phys. 2004, 205, 334.
12. (e) Bochmann, M.; Cannon, R. D.; Song, F. Kinet. Catal. 2006, 47, 160.
13. (f) Zhou, J.; Lancaster, S. J.; Walker, D. A.; Beck, S.; Thornton-Pett, M.; Bochmann, M. J. Am. Chem. Soc. 2001, 123, 223.
14. (a) Beck, S.; Geyer, A.; Brintzinger, H. H. Chem. Commun. 1999, 2477.
15. (b) Beck, S.; Lieber, S.; Schaper, F.; Geyer, A.; Brintzinger, H. H. J. Am. Chem. Soc. 2001, 123, 1483.
16. (c) Babushkin, D. E.; Brintzinger, H. H. J. Am. Chem. Soc. 2002, 124, 12869.
17. (d) Wieser, U.; Babushkin, D.; Brintzinger, H. H. Organometallics 2002, 21, 920.
18. (a) Abramo, G. P.; Li, L.; Marks, T. J. J. Am. Chem. Soc. 2002, 124, 13966.
19. (b) Stahl, N. G.; Zuccaccia, C.; Jensen, T. R.; Marks, T. J. J. Am. Chem. Soc. 2003, 125, 5256.
20. (c) Zuccaccia, G.; Stahl, N. G.; Macchioni, A.; Chen, M. C.; Roberts, J. A.; Marks, T. J. J. Am. Chem. Soc. 2004, 126, 1448.
21. Song, F.; Lancaster, S. J.; Cannon, R. D.; Schormann, M.; Humphrey, S. M.; Zuccacia, C.; Macchioni, A.; Bochmann, M. Organometallics 2005, 24, 1315.
22. (a) Horton, A. D.; Orpen, A. G. Organometallics 1992, 11, 8.
23. (b) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867.
24. (c) Carpentier, J. F.; Wu, Z.; Lee, C. W.; Strömberg, S.; Christopher, J. N.; Jordan, R. F. J. Am. Chem. Soc. 2000, 122, 7750.
25. (d) Casey, C. P.; Carpenetti, D. W. Organometallics 2000, 19, 3970.
26. (e) Casey, C. P.; Carpenetti, D. W.; Sakurai, H. Organometallics 2001, 20, 4262.
27. (f) Brandow, C. G.; Mendiratta, A.; Bercaw, J. E. Organometallics 2001, 20, 4253.
28. (a) Lui, Z.; Somsook, E.; White, C. B.; Rosaaen, A.; Landis, C. R. J. Am. Chem. Soc. 2001, 123, 11193.
29. (b) Landis, C. R.; Rosaaen, K. A.; Uddin, J. J. Am. Chem. Soc. 2002, 124, 12062.
30. (c) Landis, C. R.; Rosaeen, K. A.; Sillars, D. R. J. Am. Chem. Soc 2003, 125, 1710.
31. (d) Sillars, D. R.; Landis, C. R. J. Am. Chem. Soc. 2003, 125, 9894.
32. (e) Landis, C. R.; Sillars, D. R.; Batterton, J. M. J. Am. Chem. Soc 2004, 126, 8890.
33. (f) Busico, V.; Cipullo, R.; Romanelli, V.; Ronca, S.; Togrou, M. J. Am. Chem. Soc. 2005, 127, 1608.
34. (g) Busico, V.; Cipullo, R.; Esposito, V. Macromol. Rapid Commun. 1999, 20, 116.
35. (h) Lin, S.; Tagge, C. D.; Waymouth, R. M.; Nele, M.; Collins, S.; Pinto, J. C. J. Am. Chem. Soc 2000, 122, 11275.
36. (a) Beck, S.; Prosenc, M. H.; Brintzinger, H. H.; Goretzki, R.; Herfert, N.; Fink, G. J. Mol. Catal. A: Chem. 1996, 111, 67.
37. (b) Deck, P. A.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 6128.
38. (c) Deck, P. A.; Beswick, C. L.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 1772.
39. (d) Luo, L.; Marks, T. J. Top. Catal. 1999, 7, 97.
40. (e) Siedle, A. R.; Newmark, R. A. J. Organomet. Chem. 1995, 497, 119.
41. (f) Siedle, A. R.; Hanggi, B.; Newmark, R. A.; Mann, K. R.; Wilson, T. Macromol. Symp. 1995, 89, 299.
42. (g) Brandow, C. G.; Mendiratta, A.; Bercaw, J. E. Organometallics 2001, 20, 4253.
43. (h) Bercaw, J. E.; Miller, S. A. Organometallics 2006, 25, 3576.
44. (i) Nele, M.; Mohammed, M.; Xin, S. X.; Collins, S.; Dias, M. L.; Pinto, J. C. Macromolecules 2001, 34, 3830.
45. Song, F.; Cannon, R. D.; Bochmann, M. Chem. Commum. 2004, 542.
46. 4), has site epimerization been shown to be significantly faster than chain propagation: Mohammed, M.; Nele, M.; Al-Humydi, A.; Xin, S.; Stapleton, R. A.; Collins, S. J. Am. Chem. Soc 2003, 125, 7930.
47. Bochmann, M.; Lancaster, S. J.; Hursthouse, M. B.; Malik, K. M. A. Organometallics 1994, 13, 2235.
48. (a) Ewen, J. A.; Elder, M. J.; Jones, R. L.; Haspelagh, L.; Atwood, J. L.; Bott, S. G.; Robinson, K. Makromol. Chem. Macromol. Symp. 1991, 48/49, 253.
49. (b) Ewen, J. A.; Elder, M. J. Makromol. Chem., Macromol. Symp. 1993, 66, 179.
50. (c) Bochmann, M.; Lancaster, S. J. Organometallics 1993, 12, 633.
51. (d) Bochmann, M.; Lancaster, S. J. Macromol. Rapid Commun. 1993, 14, 807.
52. Song, F.; Cannon, R. D.; Lancaster, S. J.; Bochmann, M. J. Mol. Catal. 2004, 218, 21.
53. (a) Chen, M. C.; Marks, T. J. J. Am. Chem. Soc. 2001, 123, 11803.
54. (b) Chen, M. C.; Roberts, J. A. S.; Marks, T. J. J. Am. Chem. Soc. 2004, 126, 4605.
55. (c) Chen, M. C.; Roberts, J. A. S.; Marks, T. J. Organometallics 2004, 23, 932.
56. Ducère, J. M.; Cavallo, L. Organometallics 2006, 25, 1431.
57. Alonso-Moreno, C.; Lancaster, S. J.; Zuccaccia, C.; Macchioni, A.; Bochmann, M. J. Am. Chem. Soc. 2007, 129, 9282.
58. Ewen, J. A.; Lonew, R. L.; Razavi, A. J. Am. Chem. Soc. 1988, 110, 6255.
59. (a) Razavi, A.; Ferrara, J. J. Organomet. Chem. 1992, 435, 299.
60. (b) Razavi, A.; Thewalt, U. J. Organomet. Chem. 1993, 445, 111.
61. Hawrelak, E. J.; Deck, P. A. Organometallics 2004, 23, 9.
62. Beswick, C. L.; Marks, T. J. J. Am. Chem. Soc. 2000, 122, 10358.
63. For a definition of inner-sphere ion pairs (ISIPs) and outer-sphere ion pairs (OSIPs), see: Macchioni, A. Chem. Rev. 2005, 105, 2039.
64. (a) Yang, X.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1991, 113, 3623.
65. (b) Deck, P. A.; Beswick, C. L.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 1772.
66. (a) Bochmann, M.; Lancaster, S. J. Angew. Chem., Int. Ed. Engl. 1994, 33, 1634.
67. (b) Bochmann, M.; Lancaster, S. J. J. Organomet. Chem. 1995, 497, 55.
68. See for example: (a) Lee, H.; Hong, S. D.; Park, Y. W.; Jeong, B. G.; Nam, D. W.; Jung, H. Y.; Jung, M. W.; Song, K. H. J. Organomet. Chem. 2004, 689, 3402.
69. (b) Stahl, N. G.; Salata, M. R.; Marks, T. J. J. Am. Chem. Soc. 2005, 127, 10898.
70. 22
71. p values are therefore likely to be underestimates by a factor of 5-10.
72. 3.
73. Zuccaccia, D.; Bellachioma, G.; Cardaci, G.; Ciancaleoni, G.; Zuccaccia, C.; Clot, E.; Macchioni, A. Organometallics 2007, 26, 3930.
74. Macchioni, A. Eur. J. Inorg. Chem. 2003, 195, and references therein.
75. The experimental intensity of each interionic contact was corrected for the number of equivalent nuclei according to Macura and Ernst: Macura, S.; Ernst, R. R. Mol. Phys. 1980, 41, 95.
76. (a) Xu, Z.; Vanka, K.; Firman, T.; Michalak, A.; Zurek, E.; Zhu, C.; Ziegler, T. Organometallics 2002, 21, 2444.
77. (b) Xu, Z.; Vanka, K.; Ziegler, T. Organometallics 2004, 23, 104.
78. (c) Lanza, G.; Fragalà, I. L.; Marks, T. J. J. Am. Chem. Soc. 2000, 122, 12764.
79. (d) Lanza, G.; Fragalà, I. L.; Marks, T. J. Organometallics 2002, 21, 5594.
80. (e) Tomasi, S.; Razavi, A.; Ziegler, T. Organometallics 2007, 26, 2024.
81. i-Zr complexes and the relative energies of β-and γ-agostically bonded alkyl ligands see ref 31e.
82. (a) Bochmann, M.; Lancaster, S. J.; Hursthouse, M. B.; Mazid, M. Organometallics 1993, 12, 4718.
83. (b) Irvin, L. J.; Miller, S. A. J. Am. Chem. Soc. 2005, 127, 9972.
84. Bochmann, M.; Lancaster, S. J. J. Organomet. Chem. 1992, 434, C1.
85. (a) Massey, A. G.; Park, A. J.; Stone, F. G. A. Proc. Chem. Soc. London 1963, 212.
86. (b) Massey, A. G.; Park, A. J. J. Organomet. Chem. 1964, 2, 245.
87. Lix, B.; Sönnichsen, F. D.; Sykes, B. D. J. Magn. Reson. A 1996, 121, 83.
88. (a) Jerschow, A.; Mueller, N. J. Magn. Reson. A 1996, 123, 222.
89. (b) Jerschow, A.; Mueller, N. J. Magn. Reson. A 1997, 125, 372.
90. (c) Valentini, M.; Rüegger, H.; Pregosin, P. S Helv. Chim. Acta 2001, 84, 2833, and references therein.
91. Mills, R. J. Phys. Chem. 1973, 77, 685.
92. Macchioni, A.; Ciancaleoni, G.; Zuccaccia, C.; Zuccaccia, D. Chem. Soc. Rev. 2008, 37, 479.
93. Ciancaleoni, G.; Zuccaccia, C.; Zuccaccia, D.; Macchioni, A. Organometallics 2007, 26, 3624.
94. Otwinowski, Z.; Minor, W. In Macromolecular Crystallography, Part A; Carter, G W., Jr., Sweet, R. M., Eds.; Academic Press: New York, 1997; Methods in Enzymology Vol. 276, pp 307-326.
95. Oxford Diffraction ABSPACK, CrysAlis CCD, and CrysAlis RED, Versions 1.171; Oxford Diffraction Ltd., Abingdon, Oxford, England, 2005.
96. Sheldrick, G. M. SHELX-97: Programs for Crystal Structure Determination (SHELXS) and Refinement (SHELXL); University of Göttingen, Göttingen, Germany, 1997.
97. Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A. J. Appl. Crystallogr. 1993, 26, 343-350.
98. Beurskens, P. T.; Beurskens, G.; de Gelder, R.; Garcia-Granda, S.; Israel, R.; Gould, R. O.; Smits, J. M. M. The DIRDIF-99 Program System; Crystallography Laboratory, University of Nijmegen, Nijmegen, The Netherlands. 1999.
99. Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837.