(Cl-nacnac)Pt(H)与端炔的反应机理

doi:10.3866/PKU.WHXB20110312

Abstract

Abstract:

On the basis of Templeton′s experiment (West, N. M.; et al. Organometallics 2008, 27, 5252), the mechanisms of the main and the side reactions between (Cl-nacnac)Pt(H) (Cl-nacnac: bis(N-aryl)- β-diiminate) and a terminal alkyne were investigated by density functional theory. Our study shows that the 1,2-insertion of t-BuC≡CH into the Pt―H bond generates the main products and that C―C bond formation is the rate-determining step. The 2,1-insertion of t-BuC≡CH into the Pt―H bond generates the by- products and alkyne insertion is the rate-determining step. Based on the mechanisms of the main and side reactions the presence of the main product and the by-product could be explained. We found that the main product is thermodynamically controlled while the side product is kinetically controlled.

Key words: Density functional theory, Reaction mechanism, Pt, Alkyne insertion, Alkyne dimerization

MSC2000:

O641

WANG Jia-Yong, BI Si-Wei, ZHAO Jun-Feng. Reaction Mechanisms between (Cl-nacnac)Pt(H) and a Terminal Alkyne[J].Acta Phys. -Chim. Sin., 2011, 27(03): 571-576.

References

(1) Trost, B. M. Science 1991, 254, 1471.
(2) Nicolaou, K. C.; Dai, W. M.; Tsay, S. C.; Estevez, V. A.; Wrasidlo, W. Science 1992, 256, 1172.
(3) Hubner, H.; Haubmann, C.; Utz, W.; Gmeiner, P. J. Med. Chem. 2000, 43, 756.
(4) Trost, B. M.; Toste, D.; Pinkerton, A. Chem. Rev. 2001, 101, 2067.
(5) Bruneau, C.; Dixneuf, P. H. Accounts Chem. Res. 1999, 32, 311.
(6) Duchateau, R.; van Wee, C. T.; Teuben, J. H. Organometallics 1996, 15, 2291.
(7) Field, L. D.; Ward, A. J.; Turner, P. Aust. J. Chem. 1999, 52, 1085.
(8) Ohmura, T.; Yorozuya, S.; Yamamoto, Y.; Miyaura, N. Organometallics 2000, 19, 365.
(9) Akita, M.; Yasuda, H.; Nakamura, A. Bull. Chem. Soc. Jpn. 1984, 57, 480.
(10) Trost, B. M.; Sorum, M. T.; Chan, C.; Harms, A. E.; Ruhter, G. J. Am. Chem. Soc. 1997, 119, 698.
(11) Schafer, M.; Wolf, J.; Werner, H. Organometallics 2004, 23, 5713.
(12) Gao, Y.; Puddephatt, R. J. Inorg. Chim. Acta. 2003, 350, 101.
(13) Sans, V.; Trzeciak, A. M.; Luis, S.; Ziolkowski, J. J. Catal. Lett. 2006, 109, 37.
(14) Ananikov, V. P.; Mitchenko, S. A.; Beletskaya, I. P. J. Organomet. Chem. 2000, 604, 290.
(15) Ananikov, V. P.; Mitchenko, S. A.; Beletskaya, I. P. Russ. J. Org. Chem. 2002, 38, 636.
(16) Kong, J. R.; Krische, M. J. J. Am. Chem. Soc. 2006, 128, 16040.
(17) Bianchini, C.; Frediani, P.; Masi, D.; Peruzzini, M.; Zanobini, F.Organometallics 1994, 13, 4616.
(18) Weng, W.; Guo, C.; Celenligil-Cetin, R.; Foxman, B. M.; Ozerov, O. V. Chem. Commun. 2006, 197.
(19) Ciclosi, M.; Estevan, F.; Lahuerta, P.; Passarelli, V.; Perez-Prieto, J.; Sanau, M. Adv. Synth. Catal. 2008, 350, 234.
(20) Ghosh, R.; Zhang, X.; Achord, P.; Emge, T. J.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 2007, 129, 853.
(21) Ogoshi, S.; Ueta, M.; Oka, M. A.; Kurosawa, H. Chem. Commun. 2004, 2732
(22) Slugovc, C.; Mereiter, K.; Zobetz, E.; Schmid, R.; Kirchner, K. Organometallics 1996, 15, 5275.
(23) Li, X.; Vogel, T.; Incarvito, C. D.; Crabtree, R. H. Organometallics 2005, 24, 62.
(24) Li, X.; Incarvito, C. D.; Crabtree, R. H. J. Am. Chem. Soc. 2003, 125, 3698.
(25) Selnau, H. E.; Merola, J. S. J. Am. Chem. Soc. 1991, 113, 4008.
(26) West, N. M.; Peter, S.; Templeton, J. L. Organometallics 2008, 27, 5252.
(27) Siegbahn, P. E. M.; Blomberg, M. R. A. Annu. Rev. Phys. Chem. 1999, 50, 221.
(28) Foresman, J. B.; Frisch, M. J. Exploring Chemistry with Electrinic Structure Methods; Gaussian Inc.: Pittsburgh, PA,1993.
(29) Chong, D. P. Recent Advances in Density Functional Methods, Part I; World Scientific: Singapore, 1995.
(30) Kohn, W.; Becke, A. D.; Parr, R. G. J. Phys. Chem. 1996, 100, 12974.
(31) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
(32) Becke, A. D. Phys. Rev. A 1988, 38, 3098.
(33) Fukui, K. J. Phys. Chem. 1970, 74, 4161.
(34) Fukui, K. Acc.ounts Chem. Res. 1981, 14, 363.
(35) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B. et al. Gaussian 03, Revision B05; Gaussian, Inc.: Pittsburgh, PA, 2003.
(36) Dolg, M. Modern Methods and Algorithms of Quantum Chemistry; Grotendorst, J. Ed.; John von Neumann Institute for Computing: Jülich, Germany 2000; Vol. 1, pp 479-508.
(37) Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284.
(38) Davidson, E. R. Chem. Rev. 2000, 100, 351.
(39) Bi, S. W.; Lin, Z. Y.; Jordan, R. F. Organometallics 2004, 23, 4882.
(40) Bi, S. W.; Ariafard, A.; Jia, G. C. Organometallics 2005, 24, 680.
(41) Xue, P.; Bi, S. W.; Sung, H. Y. Organometallics 2004, 23, 4735.
(42) Ariafard, A.; Bi, S.W.; Lin, Z. Y. Organometallics 2005, 24, 2241.
(43) Zhu, X. F.; Zhao, B.; Bi, S. W. Chem. Phys. Lett. 2006, 422, 6.
(44) Bi, S. W.; Wang, B.; Gao, Y. Z. Chin. J. Inorg. Chem. 2006, 22, 13.
[毕思玮, 王宾, 高一箴. 无机化学学报 2006, 22, 13.]
(45) Fung, W. K.; Huang, X.; Man, M. L.; Ng, S. M.; Hung, M. Y.; Lin, Z.; Lau, C. P. J. Am. Chem. Soc. 2003, 125, 11539.
(46) Solin, N.; Kjellgren, J.; Szabó, K. J. J. Am. Chem. Soc. 2004, 126, 7026.
(47) Petz, W.; Kutschera, C.; Heitbaum, M.; Frenking, G.; Tonner, R.; Neumuller, B. Inorg. Chem. 2005, 44, 1263.
(48) Barton, D. H. R.; Hall, M. B.; Lin, Z.; Parekh, S. I.; Reibenspies, J. J Am. Chem. Soc. 1993, 115, 5056.
(49) West, N. M.; White, P. S.; Templeton, J. L. J. Am. Chem. Soc. 2007, 129, 12372.
(50) West, N. M.; Templeton, J. L. Can. J. Chem. 2009, 87, 288.
(51) Brookhart, M.; Green, M. L. H. J. Organomet. Chem. 1983, 250, 395.
(52) Brookhart, M.; Green, M. L. H.; Wong, L. L. Prog. Inorg. Chem. 1988, 36, 1.
(53) McGrady, G. S.; Downs, A. J. Coord. Chem. Rev. 2000, 197, 95.
(54) Zhao, H. T.; Lin, Z. Y.; Marder, T. B. J. Am. Chem. Soc. 2006, 128, 15637.
(55) Xia, Y. Z.; Huang, G. P. J. Org. Chem. 2010, 75, 7842.
(56) Sakaki, S.; Sumimato, M.; Fukuhara, M.; Sugimoto, M.; Fujimoto, H.; Matsuzaki, S. Organometallics 2002, 21, 3788.
(57) Dang, L.; Lin, Z. Y.; Marder, T. B. Organometallics 2010, 29, 917.
(58) Chen, M. J.; Nielsen, R. J.; Ahlquist, M.; Goddard, W. A. Organometallics 2010, 29, 2026.
(59) Wang, J. P.; Xu, H. Y.; Gao, H.; Su, C. Y.; Zhao, C. Y.; Phillips, D. L. Organometallics 2010, 29, 42.
(60) Liu, W. G.; Zybin, S. V.; Dasgupta, S.; Klap?otke, T. M.; Goddard, W. A., III. J. Am. Chem. Soc. 2009, 131, 7490.

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Reaction Mechanisms between (Cl-nacnac)Pt(H) and a Terminal Alkyne

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