Synthesis and applications of RuCl2(=CHR′)(PR3)2: The influence of the alkylidene moiety on metathesis activity

Journal of the American Chemical Society

Volumn 118, Issue 1, 1996, Pages 100-108

  Schwab, Peter ^a   Grubbs, Robert H ^a   Ziller, Joseph W ^b  

^a California Institute of Technology ^*  (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001855961     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja952676d     Document Type: Article

References (107)

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67. See also: (a) Szwarc, M. Carbanions, Living Polymers and Electron Transfer Processes, Wiley-Interscience: New York. 1968. (b) van Beylen, M.; Bywater, S.; Smets, G.; Szwarc, M., Worsfold, D. J. Adv. Polym. Sci. 1988, 86, 87-143. (c) Quirk, R P.; Lee, B. Polym. Int. 1992, 27, 359-367. (d) Webster, O. W. Science 1991, 251, 887-893.
68. See also: (a) Szwarc, M. Carbanions, Living Polymers and Electron Transfer Processes, Wiley-Interscience: New York. 1968. (b) van Beylen, M.; Bywater, S.; Smets, G.; Szwarc, M., Worsfold, D. J. Adv. Polym. Sci. 1988, 86, 87-143. (c) Quirk, R P.; Lee, B. Polym. Int. 1992, 27, 359-367. (d) Webster, O. W. Science 1991, 251, 887-893.
69. See also: (a) Szwarc, M. Carbanions, Living Polymers and Electron Transfer Processes, Wiley-Interscience: New York. 1968. (b) van Beylen, M.; Bywater, S.; Smets, G.; Szwarc, M., Worsfold, D. J. Adv. Polym. Sci. 1988, 86, 87-143. (c) Quirk, R P.; Lee, B. Polym. Int. 1992, 27, 359-367. (d) Webster, O. W. Science 1991, 251, 887-893.
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73. 2 (3), supposedly due to backbiting and chain transfer as side reactions.
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75. 2 (B) does not react with cyclooctatetraene.
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78. 2 (R = Me and Et) after 1 day.
79. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
80. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
81. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
82. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
83. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
84. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
85. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
86. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
87. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
88. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
89. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
90. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
91. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
92. For examples of methylidene complexes, see: (a) Brookhart, M.; Liu. Y. In Advances in Metal Carbene Chemistry; Schubert, U., Ed.; Kluwer Academic: Dordrecht, The Netherlands, 1989; Vol. 269, p 251. (b) Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6577-6578. (c) Schrock, R. R. Acc Chem Res. 1979, 12, 98-104. (d) Jolly, P. W.; Pettit, R. J. Am. Chem. Soc 1966, 88, 5044-5045. (e) Riley, P. E.; Capshew, C. E.; Pettit, R.; Davis, R. E. Inorg. Chem. 1978, 17, 408-414. (f) Bodnar, T. W.; Cutler, A. R. J. Am. Chem, Soc. 1983, 105,5926-5928. (g) Bodnar, T. W.; Cutler, A. R. Organometallics 1985, 4, 1558-1565. (h) Brookhart, M.; Nelson, G. O. J. Am. Chem. Soc. 1977, 99, 6099-6101. (i) Brookhart, M.; Tucker, J. R.; Flood, T. C.; Jensen, J. J. Am. Chem. Soc. 1980, 101, 1203-1205. (J) Guerchais, V.; Astruc, D. J. Chem. Soc., Chem. Commun. 1985, 835-837. (k) Keeley, S. E.; Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760-762. (l) Klein, D. P.; Bergman, R. G. J. Am. Chem Soc. 1989, 11, 3079-3080. (m) Holmes, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 4599-4600. (n) Hill, A. F.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Am. Chem. Soc. 1983, 105, 5939-5940.
93. (a) Fryzuk, M. D.; MacNeil, P. A.; Rettig, S J. J. Am. Chem. Soc. 1985, 107, 6708-6710.
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95. n = 59.7 kg/mol; PDI(toluene) = 1.42.
96. 2 at room temperature in 15 nun to give 4,4-diethylcyclopentene dicarboxylate quantitatively.
97. There is abundant evidence that the key step in olefin metathesis consists of the reaction between a transition metal-carbon double bond (M=CHR) and an olefin to give a metallacyclobutane ring, which was first proposed by: Hemson, J. L.; Chauvin, Y. Makromol. Chem. 1970. 141, 161.
98. Pangborn, A. B.; Nguyen, S T.; Grubbs, R. H. Unpublished results.
99. Kanaoka, S.; Grubbs, R. H. Macromolecules 1995, 28, 4707-4713.
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101. The crystal was immersed in a lube-oil additive, which allows for manipulation on the bench-top and prevents decomposition due to air or moisture. The crystal was secured to a glass fiber (the oil acts as the adhesive) which is attached to an elongated brass mounting pin. Further details were described by: Hope, H. In Experimental Organomeiailic Chemistry: A Practiciun in Synthesis and Characterization; ACS Symp. Ser. No. 357; Wayda, A. L., Darensbourg, M. Y., Eds., American Chemical Society: Washington. DC, 1987.
102. XSCANS Software Users Guide, Version 2.1, Siemens Industrial Automation, Inc., Madison, WI, 1994.
103. SHELXTL Empirical Absorption Correction program (see ref 49).
104. (a) UCLA Crystallographic Computing Package, University of California at Los Angeles, 1981.
105. (b) Strouse. C., University of California at Los Angeles, personal communication.
106. Sheldrick, G. M. Siemens Analytical X-Ray Instruments, Inc : Madison. WI, 1990.
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