(Cl-nacnac)Pt(H)与端炔的反应机理

引用本文: 王家勇, 毕思玮, 赵俊凤. (Cl-nacnac)Pt(H)与端炔的反应机理[J]. 物理化学学报, 2011, 27(03): 571-576. doi: 10.3866/PKU.WHXB20110312 shu

Citation: WANG Jia-Yong, BI Si-Wei, ZHAO Jun-Feng. Reaction Mechanisms between (Cl-nacnac)Pt(H) and a Terminal Alkyne[J]. Acta Physico-Chimica Sinica, 2011, 27(03): 571-576. doi: 10.3866/PKU.WHXB20110312 shu

(Cl-nacnac)Pt(H)与端炔的反应机理

基金项目:
山东省自然科学基金(Y2007B23) (Y2007B23)

固体表面物理化学国家重点实验室(厦门大学)(200702)资助项目 (厦门大学)(200702)

摘要:

在Templeton实验(West, N. M.; et al. Organometallics 2008, 27, 5252)的基础上, 利用密度泛函理论研究了(Cl-nacnac)Pt(H)(Cl-nacnac: bis(N-aryl)-β-diiminate)与端炔的主、副反应机理. 结果表明: 叔丁基乙炔以1,2-方式插入到Pt―H键之间生成主产物, C―C键生成为决速步骤; 以2,1-方式插入到Pt―H键之间生成副产物, 炔烃插入为决速步骤. 基于主、副反应机理, 合理地解释了主、副产物生成的原因. 分析表明, 主产物是热力学控制的产物, 而副产物是动力学控制的产物.

关键词:

English

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

1.
School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong Province, P. R. China
Received Date: 27 October 2010
Available Online: 03 March 2011
Fund Project:
山东省自然科学基金(Y2007B23)

固体表面物理化学国家重点实验室(厦门大学)(200702)资助项目

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:

1. [1]
  
  (1) Trost, B. M. Science 1991, 254, 1471.
  (1) Trost, B. M. Science 1991, 254, 1471.
2. [2]
  (2) Nicolaou, K. C.; Dai, W. M.; Tsay, S. C.; Estevez, V. A.; Wrasidlo, W. Science 1992, 256, 1172.(2) Nicolaou, K. C.; Dai, W. M.; Tsay, S. C.; Estevez, V. A.; Wrasidlo, W. Science 1992, 256, 1172.
3. [3]
  (3) Hubner, H.; Haubmann, C.; Utz, W.; Gmeiner, P. J. Med. Chem. 2000, 43, 756.(3) Hubner, H.; Haubmann, C.; Utz, W.; Gmeiner, P. J. Med. Chem. 2000, 43, 756.
4. [4]
  (4) Trost, B. M.; Toste, D.; Pinkerton, A. Chem. Rev. 2001, 101, 2067.(4) Trost, B. M.; Toste, D.; Pinkerton, A. Chem. Rev. 2001, 101, 2067.
5. [5]
  (5) Bruneau, C.; Dixneuf, P. H. Accounts Chem. Res. 1999, 32, 311.(5) Bruneau, C.; Dixneuf, P. H. Accounts Chem. Res. 1999, 32, 311.
6. [6]
  (6) Duchateau, R.; van Wee, C. T.; Teuben, J. H. Organometallics 1996, 15, 2291.(6) Duchateau, R.; van Wee, C. T.; Teuben, J. H. Organometallics 1996, 15, 2291.
7. [7]
  (7) Field, L. D.; Ward, A. J.; Turner, P. Aust. J. Chem. 1999, 52, 1085.(7) Field, L. D.; Ward, A. J.; Turner, P. Aust. J. Chem. 1999, 52, 1085.
8. [8]
  (8) Ohmura, T.; Yorozuya, S.; Yamamoto, Y.; Miyaura, N. Organometallics 2000, 19, 365.(8) Ohmura, T.; Yorozuya, S.; Yamamoto, Y.; Miyaura, N. Organometallics 2000, 19, 365.
9. [9]
  (9) Akita, M.; Yasuda, H.; Nakamura, A. Bull. Chem. Soc. Jpn. 1984, 57, 480.(9) Akita, M.; Yasuda, H.; Nakamura, A. Bull. Chem. Soc. Jpn. 1984, 57, 480.
10. [10]
  (10) Trost, B. M.; Sorum, M. T.; Chan, C.; Harms, A. E.; Ruhter, G. J. Am. Chem. Soc. 1997, 119, 698.(10) Trost, B. M.; Sorum, M. T.; Chan, C.; Harms, A. E.; Ruhter, G. J. Am. Chem. Soc. 1997, 119, 698.
11. [11]
  (11) Schafer, M.; Wolf, J.; Werner, H. Organometallics 2004, 23, 5713.(11) Schafer, M.; Wolf, J.; Werner, H. Organometallics 2004, 23, 5713.
12. [12]
  (12) Gao, Y.; Puddephatt, R. J. Inorg. Chim. Acta. 2003, 350, 101.(12) Gao, Y.; Puddephatt, R. J. Inorg. Chim. Acta. 2003, 350, 101.
13. [13]
  (13) Sans, V.; Trzeciak, A. M.; Luis, S.; Ziolkowski, J. J. Catal. Lett. 2006, 109, 37.(13) Sans, V.; Trzeciak, A. M.; Luis, S.; Ziolkowski, J. J. Catal. Lett. 2006, 109, 37.
14. [14]
  (14) Ananikov, V. P.; Mitchenko, S. A.; Beletskaya, I. P. J. Organomet. Chem. 2000, 604, 290.(14) Ananikov, V. P.; Mitchenko, S. A.; Beletskaya, I. P. J. Organomet. Chem. 2000, 604, 290.
15. [15]
  (15) Ananikov, V. P.; Mitchenko, S. A.; Beletskaya, I. P. Russ. J. Org. Chem. 2002, 38, 636.(15) Ananikov, V. P.; Mitchenko, S. A.; Beletskaya, I. P. Russ. J. Org. Chem. 2002, 38, 636.
16. [16]
  (16) Kong, J. R.; Krische, M. J. J. Am. Chem. Soc. 2006, 128, 16040.(16) Kong, J. R.; Krische, M. J. J. Am. Chem. Soc. 2006, 128, 16040.
17. [17]
  (17) Bianchini, C.; Frediani, P.; Masi, D.; Peruzzini, M.; Zanobini, F.Organometallics 1994, 13, 4616.(17) Bianchini, C.; Frediani, P.; Masi, D.; Peruzzini, M.; Zanobini, F.Organometallics 1994, 13, 4616.
18. [18]
  (18) Weng, W.; Guo, C.; Celenligil-Cetin, R.; Foxman, B. M.; Ozerov, O. V. Chem. Commun. 2006, 197.(18) Weng, W.; Guo, C.; Celenligil-Cetin, R.; Foxman, B. M.; Ozerov, O. V. Chem. Commun. 2006, 197.
19. [19]
  (19) Ciclosi, M.; Estevan, F.; Lahuerta, P.; Passarelli, V.; Perez-Prieto, J.; Sanau, M. Adv. Synth. Catal. 2008, 350, 234.(19) Ciclosi, M.; Estevan, F.; Lahuerta, P.; Passarelli, V.; Perez-Prieto, J.; Sanau, M. Adv. Synth. Catal. 2008, 350, 234.
20. [20]
  (20) Ghosh, R.; Zhang, X.; Achord, P.; Emge, T. J.; Krogh-Jespersen, K.; ldman, A. S. J. Am. Chem. Soc. 2007, 129, 853.(20) Ghosh, R.; Zhang, X.; Achord, P.; Emge, T. J.; Krogh-Jespersen, K.; ldman, A. S. J. Am. Chem. Soc. 2007, 129, 853.
21. [21]
  (21) O shi, S.; Ueta, M.; Oka, M. A.; Kurosawa, H. Chem. Commun. 2004, 2732(21) O shi, S.; Ueta, M.; Oka, M. A.; Kurosawa, H. Chem. Commun. 2004, 2732
22. [22]
  (22) Slu vc, C.; Mereiter, K.; Zobetz, E.; Schmid, R.; Kirchner, K. Organometallics 1996, 15, 5275.(22) Slu vc, C.; Mereiter, K.; Zobetz, E.; Schmid, R.; Kirchner, K. Organometallics 1996, 15, 5275.
23. [23]
  (23) Li, X.; Vogel, T.; Incarvito, C. D.; Crabtree, R. H. Organometallics 2005, 24, 62.(23) Li, X.; Vogel, T.; Incarvito, C. D.; Crabtree, R. H. Organometallics 2005, 24, 62.
24. [24]
  (24) Li, X.; Incarvito, C. D.; Crabtree, R. H. J. Am. Chem. Soc. 2003, 125, 3698.(24) Li, X.; Incarvito, C. D.; Crabtree, R. H. J. Am. Chem. Soc. 2003, 125, 3698.
25. [25]
  (25) Selnau, H. E.; Merola, J. S. J. Am. Chem. Soc. 1991, 113, 4008.(25) Selnau, H. E.; Merola, J. S. J. Am. Chem. Soc. 1991, 113, 4008.
26. [26]
  (26) West, N. M.; Peter, S.; Templeton, J. L. Organometallics 2008, 27, 5252.(26) West, N. M.; Peter, S.; Templeton, J. L. Organometallics 2008, 27, 5252.
27. [27]
  (27) Siegbahn, P. E. M.; Blomberg, M. R. A. Annu. Rev. Phys. Chem. 1999, 50, 221.(27) Siegbahn, P. E. M.; Blomberg, M. R. A. Annu. Rev. Phys. Chem. 1999, 50, 221.
28. [28]
  (28) Foresman, J. B.; Frisch, M. J. Exploring Chemistry with Electrinic Structure Methods; Gaussian Inc.: Pittsburgh, PA,1993.(28) Foresman, J. B.; Frisch, M. J. Exploring Chemistry with Electrinic Structure Methods; Gaussian Inc.: Pittsburgh, PA,1993.
29. [29]
  (29) Chong, D. P. Recent Advances in Density Functional Methods, Part I; World Scientific: Singapore, 1995.(29) Chong, D. P. Recent Advances in Density Functional Methods, Part I; World Scientific: Singapore, 1995.
30. [30]
  (30) Kohn, W.; Becke, A. D.; Parr, R. G. J. Phys. Chem. 1996, 100, 12974.(30) Kohn, W.; Becke, A. D.; Parr, R. G. J. Phys. Chem. 1996, 100, 12974.
31. [31]
  (31) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.(31) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
32. [32]
  (32) Becke, A. D. Phys. Rev. A 1988, 38, 3098.(32) Becke, A. D. Phys. Rev. A 1988, 38, 3098.
33. [33]
  (33) Fukui, K. J. Phys. Chem. 1970, 74, 4161.(33) Fukui, K. J. Phys. Chem. 1970, 74, 4161.
34. [34]
  (34) Fukui, K. Acc.ounts Chem. Res. 1981, 14, 363.(34) Fukui, K. Acc.ounts Chem. Res. 1981, 14, 363.
35. [35]
  (35) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B. et al. Gaussian 03, Revision B05; Gaussian, Inc.: Pittsburgh, PA, 2003.(35) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B. et al. Gaussian 03, Revision B05; Gaussian, Inc.: Pittsburgh, PA, 2003.
36. [36]
  (36) Dolg, M. Modern Methods and Al rithms of Quantum Chemistry; Grotendorst, J. Ed.; John von Neumann Institute for Computing: Jülich, Germany 2000; Vol. 1, pp 479-508.(36) Dolg, M. Modern Methods and Al rithms of Quantum Chemistry; Grotendorst, J. Ed.; John von Neumann Institute for Computing: Jülich, Germany 2000; Vol. 1, pp 479-508.
37. [37]
  (37) Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284.(37) Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284.
38. [38]
  (38) Davidson, E. R. Chem. Rev. 2000, 100, 351.(38) Davidson, E. R. Chem. Rev. 2000, 100, 351.
39. [39]
  (39) Bi, S. W.; Lin, Z. Y.; Jordan, R. F. Organometallics 2004, 23, 4882.(39) Bi, S. W.; Lin, Z. Y.; Jordan, R. F. Organometallics 2004, 23, 4882.
40. [40]
  (40) Bi, S. W.; Ariafard, A.; Jia, G. C. Organometallics 2005, 24, 680.(40) Bi, S. W.; Ariafard, A.; Jia, G. C. Organometallics 2005, 24, 680.
41. [41]
  (41) Xue, P.; Bi, S. W.; Sung, H. Y. Organometallics 2004, 23, 4735.(41) Xue, P.; Bi, S. W.; Sung, H. Y. Organometallics 2004, 23, 4735.
42. [42]
  (42) Ariafard, A.; Bi, S.W.; Lin, Z. Y. Organometallics 2005, 24, 2241.(42) Ariafard, A.; Bi, S.W.; Lin, Z. Y. Organometallics 2005, 24, 2241.
43. [43]
  (43) Zhu, X. F.; Zhao, B.; Bi, S. W. Chem. Phys. Lett. 2006, 422, 6.(43) Zhu, X. F.; Zhao, B.; Bi, S. W. Chem. Phys. Lett. 2006, 422, 6.
44. [44]
  (44) Bi, S. W.; Wang, B.; Gao, Y. Z. Chin. J. Inorg. Chem. 2006, 22, 13.(44) Bi, S. W.; Wang, B.; Gao, Y. Z. Chin. J. Inorg. Chem. 2006, 22, 13.
45. [45]
  [毕思玮, 王宾, 高一箴. 无机化学学报 2006, 22, 13.][毕思玮, 王宾, 高一箴. 无机化学学报 2006, 22, 13.]
46. [46]
  (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.(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.
47. [47]
  (46) Solin, N.; Kjellgren, J.; Szabó, K. J. J. Am. Chem. Soc. 2004, 126, 7026.(46) Solin, N.; Kjellgren, J.; Szabó, K. J. J. Am. Chem. Soc. 2004, 126, 7026.
48. [48]
  (47) Petz, W.; Kutschera, C.; Heitbaum, M.; Frenking, G.; Tonner, R.; Neumuller, B. Inorg. Chem. 2005, 44, 1263.(47) Petz, W.; Kutschera, C.; Heitbaum, M.; Frenking, G.; Tonner, R.; Neumuller, B. Inorg. Chem. 2005, 44, 1263.
49. [49]
  (48) Barton, D. H. R.; Hall, M. B.; Lin, Z.; Parekh, S. I.; Reibenspies, J. J Am. Chem. Soc. 1993, 115, 5056.(48) Barton, D. H. R.; Hall, M. B.; Lin, Z.; Parekh, S. I.; Reibenspies, J. J Am. Chem. Soc. 1993, 115, 5056.
50. [50]
  (49) West, N. M.; White, P. S.; Templeton, J. L. J. Am. Chem. Soc. 2007, 129, 12372.(49) West, N. M.; White, P. S.; Templeton, J. L. J. Am. Chem. Soc. 2007, 129, 12372.
51. [51]
  (50) West, N. M.; Templeton, J. L. Can. J. Chem. 2009, 87, 288.(50) West, N. M.; Templeton, J. L. Can. J. Chem. 2009, 87, 288.
52. [52]
  (51) Brookhart, M.; Green, M. L. H. J. Organomet. Chem. 1983, 250, 395.(51) Brookhart, M.; Green, M. L. H. J. Organomet. Chem. 1983, 250, 395.
53. [53]
  (52) Brookhart, M.; Green, M. L. H.; Wong, L. L. Prog. Inorg. Chem. 1988, 36, 1.(52) Brookhart, M.; Green, M. L. H.; Wong, L. L. Prog. Inorg. Chem. 1988, 36, 1.
54. [54]
  (53) McGrady, G. S.; Downs, A. J. Coord. Chem. Rev. 2000, 197, 95.(53) McGrady, G. S.; Downs, A. J. Coord. Chem. Rev. 2000, 197, 95.
55. [55]
  (54) Zhao, H. T.; Lin, Z. Y.; Marder, T. B. J. Am. Chem. Soc. 2006, 128, 15637.(54) Zhao, H. T.; Lin, Z. Y.; Marder, T. B. J. Am. Chem. Soc. 2006, 128, 15637.
56. [56]
  (55) Xia, Y. Z.; Huang, G. P. J. Org. Chem. 2010, 75, 7842.(55) Xia, Y. Z.; Huang, G. P. J. Org. Chem. 2010, 75, 7842.
57. [57]
  (56) Sakaki, S.; Sumimato, M.; Fukuhara, M.; Sugimoto, M.; Fujimoto, H.; Matsuzaki, S. Organometallics 2002, 21, 3788.(56) Sakaki, S.; Sumimato, M.; Fukuhara, M.; Sugimoto, M.; Fujimoto, H.; Matsuzaki, S. Organometallics 2002, 21, 3788.
58. [58]
  (57) Dang, L.; Lin, Z. Y.; Marder, T. B. Organometallics 2010, 29, 917.(57) Dang, L.; Lin, Z. Y.; Marder, T. B. Organometallics 2010, 29, 917.
59. [59]
  (58) Chen, M. J.; Nielsen, R. J.; Ahlquist, M.; ddard, W. A. Organometallics 2010, 29, 2026.(58) Chen, M. J.; Nielsen, R. J.; Ahlquist, M.; ddard, W. A. Organometallics 2010, 29, 2026.
60. [60]
  (59) Wang, J. P.; Xu, H. Y.; Gao, H.; Su, C. Y.; Zhao, C. Y.; Phillips, D. L. Organometallics 2010, 29, 42.(59) Wang, J. P.; Xu, H. Y.; Gao, H.; Su, C. Y.; Zhao, C. Y.; Phillips, D. L. Organometallics 2010, 29, 42.
61. [61]
  (60) Liu, W. G.; Zybin, S. V.; Dasgupta, S.; Klap?otke, T. M.; ddard, W. A., III. J. Am. Chem. Soc. 2009, 131, 7490.
  (60) Liu, W. G.; Zybin, S. V.; Dasgupta, S.; Klap?otke, T. M.; ddard, W. A., III. J. Am. Chem. Soc. 2009, 131, 7490.

扫一扫看文章

计量

PDF下载量: 1013
文章访问数: 3735
HTML全文浏览量: 67

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

(Cl-nacnac)Pt(H)与端炔的反应机理

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

(Cl-nacnac)Pt(H)与端炔的反应机理

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs