Structural and spectroscopic demonstration of agostic C-C interactions in electron-deficient metallacyclobutanes and related cage complexes: Possible implications for olefin polymerizations and metatheses

Journal of the American Chemical Society

Volumn 127, Issue 47, 2005, Pages 16426-16435

  Harvey, Benjamin G ^a   Mayne, Charles L ^a   Arif, Atta M ^a   Ernst, Richard D ^a  

^a UNIVERSITY OF UTAH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BUTANE; COMPLEXATION; MOLECULAR STRUCTURE; OLEFINS; POLYMERIZATION; TITANIUM COMPOUNDS; X RAY DIFFRACTION;

ALLYL FRAGMENTS; C-H BOND; COUPLING REACTIONS;

ORGANOMETALLICS;

ALKENE; CYCLOBUTANE DERIVATIVE; MOLYBDENUM; TITANIUM; TITANOCENE; TUNGSTEN;

ARTICLE; CHEMICAL BOND; COMPLEX FORMATION; CRYSTALLIZATION; DENSITY; POLYMERIZATION; SPECTROSCOPY; X RAY DIFFRACTION;

EID: 28444486339     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja052287b     Document Type: Article

References (112)

1. Kubas, G. J. Metal Dihydrogen and σ-bond Complexes; Kluwer Academic/Plenum Publishers: New York, 2001.
2. See: Dzwiniel, T. L.; Stryker, J. M. J. Am. Chem. Soc. 2004, 126, 9184 and references therein.
3. (a) Low, J. J.; Goddard, W. A., III. J. Am. Chem. Soc. 1984, 106, 10779.
4. (b) Blomberg, M. R. A.; Siegbahn, P. E. M.; Nagashima, U.; Wennerberg, J. J. Am. Chem. Soc. 1991, 113, 424.
5. Siegbahn, P. E. M.; Blomberg, M. R. A. J. Am. Chem. Soc. 1992, 114, 10548.
6. Rybtchinski, B.; Oevers, S.; Montag, M.; Vigalok, A.; Rozenberg, H.; Martin, J. M. L.; Milstein, D. J. Am. Chem. Soc. 2001, 123, 9064.
7. (e) Hinrichs, R. Z.; Schroden, J. J.; Davis, H. F. J. Am. Chem. Soc. 2003, 125, 860.
8. Crabtree, R. H.; Holt, E. M.; Lavin, M.; Morehouse, S. M. Inorg. Chem. 1985, 24, 1986
9. Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1988, 110, 108.
10. (a) Wilson, A. M.; Waldman, T. E.; Rheingold, A. L.; Ernst, R. D. J. Am. Chem. Soc. 1992, 114, 6252.
11. (b) Tomaszewski, R.; Hyla-Kryspin, I.; Mayne, C. L.; Arif, A. M.; Gleiter, R.; Ernst, R. D. J. Am. Chem. Soc. 1998, 120, 2959.
12. Newbound, T. D.; Stahl, L.; Ziegler, M. L.; Ernst, R. D. Organometallics 1990, 9, 2962.
13. Straus, D. A.; Grubbs, R. H. Organometallics 1982, 1, 1658.
14. (a) Carter. C. A. G.; Greidanus, G.; Chen, J.-X.; Stryker, J. M. J. Am. Chem. Soc. 2001, 123, 8872.
15. (b) Casty, G. L.; Stryker, J. M. J. Am. Chem. Soc. 1995, 117, 7814.
16. Tjaden, E. B.; Stryker, J. M. J. Am. Chem. Soc. 1993, 115, 2083.
17. Fitzmaurice, N. J.; Jackson, W. R.; Perlmutter, P. J. Organomet. Chem. 1985, 285, 375.
18. Jackson, W. R.; McMule, C. H.; Spratt, R.; Bladen, P. J. Organomet. Chem. 1965, 4, 392.
19. Benson, R. E.; McKusick, B. C. Organic Syntheses; Wiley: New York, 1963; Collect. Vol. IV, p 1746.
20. Ephrilikhine, M.; Francis, B. R.; Green, M. L. H.; Mackenzie, R. E.; Smith, M. J. J. Chem. Soc., Dalton Trans. 1977, 1131.
21. Kulsomphob, V.; Tomaszewski, R.; Yap, G. P. A.; Liable-Sands, L. M.; Rheingold, A. L.; Ernst, R. D. J. Chem. Soc., Dalton Trans. 1999, 3995.
22. Mach, K.; Troyanov, S. I. J. Organomet. Chem. 1991, 414, C15.
23. (a) Basta, R.; Arif, A. M.; Ernst, R. D. Organometallics 2003, 22, 812.
24. (b) Herbert, B. J.; Baik, M.-H.; Green, J. C. Organometallics 2004, 23, 2658.
25. (a) Rivera, A. V.; Sheldrick, G. M. Acta Crystallogr. 1978, 34B, 1716.
26. (b) Blümel, J.; Hertkorn, N.; Kanellakopulos, B.; Köhler, F.; Lachmann, J.; Müller, G.; Wagner, F. E. Organometallics 1993, 12, 3896.
27. (c) Chung, H.-J.; Sheridan, J. B.; Coté, M. L.; Lalancette, R. A. Organometallics 1996, 15, 4575.
28. (a) Cotton, F. A.; Day, V. W. J. Chem. Soc., Chem. Commun. 1974, 415.
29. (b) Cotton, F. A.; LaCour, T.; Stanislowski, A. G. J. Am. Chem. Soc. 1974, 96, 754.
30. (a) Brookhart, M. S.; Green, M. L. H.; Wong, L. L. Prog. Inorg. Chem. 1988, 36, 1.
31. (b) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789.
32. Wray, V.; Hansen, P. E. (Webb, C. A., Ed.) Ann. Rep. NMR Spectrosc. 1981, 11A, 99.
33. Maseras, F.; Crabtree, R. H. Inorg. Chim. Acta 2004, 357, 345.
34. (a) Bochmann, M. In Comprehensive Organometallic Chemistry II; Abel, E. W.; Stone, F. G. A.; Wilkinson, G., Eds; Elsevier: New York, 1995; Vol. 4, pp 222, 274.
35. (b) Binger, P.; Podubrin, S. Comprehensive Organometallic Chemistry II; Abel, E. W.; Stone, F. G. A.; Wilkinson, G., Eds; Elsevier: New York, 1995; Vol. 4, p 439.
36. (a) Structural representations of such intermediates have been depicted with as many as five dashed lines, for example:
37. (b) Piers, W. E.; Bercaw, J. E. J. Am. Chem. Soc. 1990, 112, 9406.
38. As pointed out by a reviewer, the agostic species would not necessarily be intermediates in that they do not need to be local minima in an energetic sense.
39. (a) Ivin, K. J.; Rooney, J. J.; Stewart, C. D.; Green, M. L. H.; Mahtab, R. J. Chem. Soc., Chem. Commun. 1978, 604.
40. (b) Chirik, P. J.; Dalleska, N. F.; Henling, L. M.; Bercaw, J. E. Organometallics 2005, 24, 2789.
41. Ernst, R. D. Comments Inorg. Chem. 1999, 21, 285.
42. Harvey, B. G. Ph.D. Thesis, University of Utah, 2005.
43. (a) Tillack, A.; Baumann, W.; Ohff, A.; Lefeber, C.; Spannenberg, A.; Kempe, R.; Rosenthal, U. J. Organomet. Chem. 1996, 520, 187.
44. (b) Rosenthal, U.; Pellny, P.-M.; Kirchbauer, F. G.; Burlakov, V. V. Acc. Chem. Res. 2000, 33, 119.
45. (a) Seetz, J. W. F. L.; van de Heisteeg, B. J.; Schat, G.; Akkerman, O. S.; Bickelhaupt, F. J. Mol. Catal. 1985, 28, 71.
46. (b) Seetz, J. W. F. L.; Schat, G.; Akkerman, O. S.; Bickelhaupt, F. Angew. Chem., Suppl. 1983, 234.
47. (c) de Boer, H. J. R.; van de Heisteeg, B. J. J.; Schat, G.; Akkerman, O. S.; Bickelhaupt, F. J. Organomet. Chem. 1988, 346, 197.
48. Feldman, J.; Davis, W. M.; Thomas, J. K.; Schrock, R. R. Organometallics 1990, 9, 2535.
49. (a) Lee, J. B.; Gajda, G. J.; Schaefer, W. P.; Howard, T. R.; Ikariya, T.; Straus, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 1981, 103, 7358.
50. (b) Stille, J. R.; Santarsiero, B. D.; Grubbs, R. H. J. Org. Chem. 1990, 55, 843.
51. (c) Beckhaus, R.; Flatau, S.; Trojanov, S.; Hofmann, P. Chem. Ber. 1992, 125, 291.
52. (d) Brinkmann, P. H. P.; Prosenc, M.-H.; Luinstra, G. A. Organometallics 1995, 14, 5481.
53. (e) Polse, J. L.; Kaplan, A. W.; Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1998, 120, 6316.
54. (f) Greidanus, G.; McDonald, R.; Stryker, J. M. Organometallics 2001, 20, 2492.
55. An α-benzyl-substituted zirconium complex has been structurally characterized:
56. Binger, P.; Müller, P.; Podybrin, S.; Albus, S.; Krüger, C. J. Organomet. Chem. 2002, 656, 288.
57. Schrock, R. R.; DcPue, R. T.; Feldman, J.; Schaverien, C. J.; Dewan, J. C.; Liu, A. H. J. Am. Chem. Soc. 1988, 110, 1423.
58. The presence of the phenyl and trimethylsilyl substituents would in fact stabilize a metallacyclopropane resonance contribution.
59. Baldridge, K. K.; Kasahara, Y.; Ogawa, K.; Siegel, J. S.; Tanaka, K.; Toda, F. J. Am. Chem. Soc. 1998, 120, 6167.
60. Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789.
61. Tjaden, E. B.; Schwiebert, K. E.; Stryker, J. M. J. Am. Chem. Soc. 1992, 114, 1100.
62. Cardin, D. J.; Lappert, M. F.; Raston, C. L. Chemistry of Organo-zirconium and -Hafnium Compounds; Eilis Horwood: Chichester, UK, 1986.
63. (a) Katz. T. J. Adv. Organomet. Chem. 1977, 16, 283.
64. (b) Ring Opening Polymerization: Mechanisms, Catalysis, Structure, Utility, Brunelle, D. J., Ed.; Hanser Publishers: Munich, 1993.
65. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036.
66. Alkene Metathesis in Organic Synthesis. In Topics in Organometallic Chemistry; Fürstner, A., Ed.; Springer: Berlin, 1998.
67. (e) Metathesis Polymerization of Olefins and Polymerization of Alkynes; Imamoglu, Y., Ed.; NATO Advanced Study Institute Series C506; Kluwer Academic Publishers: Norwell, MA, 1998.
68. (f) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18.
69. (g) Schrock, R. R.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2003, 42, 45.
70. (h) Handbook of Metathesis; Grubbs, R. H., Ed.; Wiley: New York, 2003.
71. (i) Grubbs, R. H.; Trnka, T. M.; Sanford, M. S. In Current Methods in Inorganic Chemistry; Kurosawa, H., Yamamoto, A., Eds.; Elsevier: New York, 2003; Vol. 3, p 187.
72. (j) Grubbs, R. H. Tetrahedron 2004, 60, 7117.
73. (k) Hoveyda, A. H.; Schrock, R. R. Comp. Asym. Catal., Suppl. 2004, 1, 207.
74. (l) Adlhart, C.; Volland, M. A. O.; Hofmann, P.; Chen, P. Helv. Chim. Acta 2000, 83, 3306.
75. Note that the reversion of a metallacyclobutane to an olefin and a metal carbene has indeed produced the expected products of both an α and a β elimination.
76. (a) Vyboishchikov, S. F.; Bühl, M.; Thiel, W. Chem. Eur. J. 2002, 8, 3962.
77. (b) Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997, 119, 3887.
78. (c) Ulman, M.; Grubbs, R. H. Organometallics 1998, 17, 2484.
79. (d) Aagard, O. M.; Meier, R. J.; Buda, F. J. Am. Chem. Soc. 1998, 120, 7174.
80. (e) Adlhart, C.; Hinderling, C.; Baumann, H.; Chen, P. J. Am. Chem. Soc. 2000, 122, 8204.
81. (f) Cavallo, L. J. Am. Chem. Soc. 2002, 124, 8965.
82. (g) Bernardi, F.; Bottoni, A.; Miscione, G. P. Organometallics 2003, 22, 940.
83. (h) Sanford, M. S.; Ullman, M.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 749.
84. (i) Sanford, M. S.; Love, J. A. Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 6543.
85. (j) Adlhart, C.; Chen, P. J. Am. Chem. Soc. 2004, 126, 3496.
86. (k) Hansen, S. M.; Rominser, F.; Metz, M.; Hofmann, P. Chem. Eur. J. 1999, 5, 557.
87. Suresh, C. H.; Koga, N. Organometallics 2004, 23, 76.
88. Romero, P. E.; Piers, W. E. J. Am. Chem. Soc. 2005. 127, 5032.
89. (a) Tomaszewski, R.; Arif, A. M.; Ernst, R. D. J. Chem. Soc., Dalton Trans. 1999, 1883.
90. (b) Dobado, J. A.; Molina, J. M.; Uggle, R.; Sundberg, M. R. Inorg. Chem. 2000, 39, 2831.
91. (a) Schrock, R. R. Acc. Chem. Res. 1990, 23, 158.
92. (b) Feldman, J.; Murdzek, J. S.; Davis, W. M.; Schroek, R. R. Organometallics 1989, 8, 2260.
93. (a) Hartwig, J. F.; Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1990, 112, 5670.
94. (b) Diversi, P.; Ingrosso, G.; Lucherini, A.; Marchetti, F.; Adovasio, V.; Nardelli, M. J. Chem. Soc., Dalton Trans. 1991, 203.
95. (c) Steltser, N. A.; Rybin, L. V.; Petrovskaya, E. A.; Batsanov, A. S.; Dzhafarov, M. Kh.; Struehkov, Yu. T.; Rybinskaya, M. I.; Petrovskii, P. V. Metallorg. Khim. (Russ.) 1992, 5, 1009.
96. (d) McNeill, K.; Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1997, 119, 11244.
97. (a) Bazan, G. C.; Khosravi, E.; Schrock, R. R.; Feast, W. J.; Gibson, V. C.; O'Regan, M. B.; Thomas, J. K.; Davis, W. M. J. Am. Chem. Soc. 1990, 112, 8378.
98. (b) Bazan, G. C.; Oskam, J. H.; Cho, H.-N.; Park, L. Y.; Schrock, R. R. J. Am. Chem. Soc. 1991, 113, 6899.
99. (c) Tsang, W. C. P.; Hultzsch, K. C.; Alexander, J. B.; Bonitatebus, P. J., Jr.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 2652.
100. (d) Hao, S.; Song, J.-I.; Berno, P.; Gambarotta, S. Organometallics 1994, 13, 1326.
101. One issue which has not been addressed here relates to the fact that the coupling constants for differing types of bonds (H-H, C-H, C-C) would not be expected to respond identically to their involvement in agostic interactions: i.e., a 30% decrease in coupling constant for different bonds would not he expected to correspond to identical decreases in bond order or strength.
102. It is also to be expected that even in cases of interactions primarily involving C-H bonds, there could be weaker C-C interactions as well, in essence leading to a continuum of possibilities in which the relative C-H and C-C contributions vary.
103. See, for example: Haaland, A.; Scherer, W.; Ruud, K.; McGrady, G. S.; Downs, A. J.; Swang, O. J. Am. Chem. Soc. 1998, 120, 3762.
104. Goldfuss, B.; Schleyer, P. v. R.; Hampel, F. J. Am. Chem. Soc. 1996, 118, 12183.
105. Jaffart, J.; Etienne, M.; Reinhold, M.; McGrady, J. E.; Maseras, F. J. Chem. Soc., Chem. Commun. 2003, 876.
106. (a) Eshius, J. J. W.; Tan, Y. Y.; Meetsma, A.; Teuben, J. H.; Renkema, J.; Evens, G. G. Organometallics 1992, 11, 362.
107. (b) Yang, X.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015.
108. (c) Corker, J.; Lefebvre, F.; Lȩcuyer, C.; Dufaud, V.; Quignard, F.; Choplin, A.; Evans, J.; Basset, J.-M. Science 1996, 271, 966.
109. (d) Resconi, L.; Piemontesi, F.; Franciscono, G.; Abis, L.; Fioriani, T. J. Am. Chem. Soc. 1992, 114, 1025.
110. (e) Lanza, G.; Fragalà, I. L.; Marks, T. J. J. Am. Chem. Soc. 2000, 122, 12764.
111. (f) Horton, A. D. Organometallics 1996, 15, 2675.
112. 3 units. See ref 1, pp 121-128, 188-194.