Citation: ZENG Xiao-Lan, WANG Yan. Mechanism and Regioselectivity of Addition Reactions of CH₃OH to Germasilenes[J]. Acta Physico-Chimica Sinica, ;2015, 31(9): 1699-1707. doi: 10.3866/PKU.WHXB201507202 shu

Mechanism and Regioselectivity of Addition Reactions of CH₃OH to Germasilenes

ZENG Xiao-Lan ,
WANG Yan

1.
College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000, Henan Province, P. R. China

Received Date: 7 May 2015
Available Online: 20 July 2015
Fund Project: 河南省基础与前沿技术研究计划(142300410194)资助项目 (142300410194)

Density functional theory (DFT) calculations of the reaction mechanisms and potential energy surfaces for the addition reactions of CH₃OH to several germasilenes were performed at the B3LYP/6-311++G(d,p) level. The effect of the polarity of the Si=Ge double bond in germasilenes on the regioselectivity of the addition reactions was also investigated. The results indicate that germasilenes can react with a monomer or dimer of CH₃OH. All reactions start with formation of nucleophilic or electrophilic complexes. The dimer of CH₃OH adds to H₂Si=GeH₂ kinetically more easily than the monomer. However, the situation is generally the opposite for substituted germasilenes. There is a kinetic disadvantage of substituting phenyl (Ph) or SiMe₃ groups for H atoms in H₂Si=GeH₂ in the addition reactions, and the effect of the SiMe₃ group is more remarkable than that of the Ph substituent. Both the polarity of the Si=Ge double bond and the strength of the Si-O (Ge-H) and Ge-O (Si-H) bonds affect the regioselectivity of the addition reactions.
- Germasilene,
- Addition reaction,
- Reaction mechanism,
- Density functional theory,
- Regioselectivity
1. [1]
  
  (1) West, R.; Fink, M. J.; Michl, J. Science 1981, 214, 1343. doi: 10.1126/science.214.4527.1343
2. [2]
  (2) Baines, K. M.; Cooke, J. A. Organometallics 1991, 10, 3419. doi: 10.1021/om00056a004
3. [3]
  (3) Lee, V. Y.; Ichinohe, M.; Sekiguchi, A.; Takagi, N.; Nagase, S. J. Am. Chem. Soc. 2000, 122, 9034. doi: 10.1021/ja001551s
4. [4]
  (4) Lee, V. Y.; Ichinohe, M.; Sekiguchi, A. J. Am. Chem. Soc. 2000, 122, 12604. doi: 10.1021/ja0030921
5. [5]
  (5) Ichinohe, M.; Arai, Y.; Sekiguchi, A.; Takagi, N.; Nagase, S. Organometallics 2001, 20, 4141. doi: 10.1021/om010419d
6. [6]
  (6) Sekiguchi, A.; Izumi, R.; Ihara, S.; Ichinohe, M.; Lee, V. Y. Angew. Chem. Int. Edit. 2002, 41, 1598. doi: 10.1002/1521-3773(20020503)41:9<1598::AID-ANIE1598>3.0.CO;2-8
7. [7]
  (7) Iwamoto, T.; Masuda, H.; Kabuto, C.; Kira, M. Organometallics 2005, 24, 197. doi: 10.1021/om049183e
8. [8]
  (8) Iwamoto, T.; Abe, T.; Kabuto, C.; Kira, M. Chem. Commun. 2005, 5190.
9. [9]
  (9) Igarashi, M.; Ichinohe, M.; Sekiguchi, A. Heteroat. Chem. 2008, 19, 649. doi: 10.1002/hc.v19:7
10. [10]
  (10) Iwamoto, T.; Okita, J.; Yoshida, N.; Kira, M. Silicon 2010, 2, 209. doi: 10.1007/s12633-011-9069-8
11. [11]
  (11) Grev, R. S.; Schaefer, H. F., III; Baines, K. M. J. Am. Chem. Soc. 1990, 112, 9458. doi: 10.1021/ja00182a003
12. [12]
  (12) Grev, R. S.; Schaefer, H. F., III. Organometallics 1992, 11, 3489. doi: 10.1021/om00059a002
13. [13]
  (13) Apeloig, Y.; Nakash, M. Organometallics 1998, 17, 2307. doi: 10.1021/om980016m
14. [14]
  (14) Takahashi, M.; Veszprémi, T.; Hajgató, B.; Kira, M. Organometallics 2001, 19, 4660. doi: 10.1021/om000385u
15. [15]
  (15) Veszprémi, T.; Takahashi, M.; Hajgató, B.; Kira, M. J. Am. Chem. Soc. 2001, 123, 6629. doi: 10.1021/ja0040823
16. [16]
  (16) Takahashi, M.; Veszprémi, T.; Kira, M. Organometallics 2004, 23, 5768. doi: 10.1021/om049418m
17. [17]
  (17) Yamabe, S.; Mizukami, N.; Tsuchida, N.; Yamazaki, S. J. Organomet. Chem. 2008, 693, 1335. doi: 10.1016/j.jorganchem.2008.01.035
18. [18]
  (18) Li, B. Y.; Su, M. D. J. Phys. Chem. A 2012, 116, 4222. doi: 10.1021/jp3018138
19. [19]
  (19) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
20. [20]
  (20) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785
21. [21]
  (21) Cossi, M.; Barone, V.; Cammi, R.; Tomasi, J. Chem. Phys. Lett. 1996, 255, 327. doi: 10.1016/0009-2614(96)00349-1
22. [22]
  (22) Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735. doi: 10.1063/1.449486
23. [23]
  (23) Reed, A. E.; Weinhold, F. J. Chem. Phys. 1985, 83, 1736. doi: 10.1063/1.449360
24. [24]
  (24) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al. Gaussian 09, Revision A.02; Gaussian Inc.: Wallingford, CT, 2009.
25. [25]
  (25) Wang, X.; Huang, Y.; An, K.; Fan, J.; Zhu, J. J. Organomet. Chem. 2014, 770, 146. doi: 10.1016/j.jorganchem.2014.08.018
26. [26]
  (26) Wang, X.; Zhu, C.; Xia, H.; Zhu, J. Organometallics 2014, 33, 1845. doi: 10.1021/om500170w
27. [27]
  (27) Huang, Y.; Zhu, J. Chem. Asian J. 2015, 10, 405. doi: 10.1002/asia.v10.2
28. [28]
  (28) Zhou, Z. Y.; Liu, M.; Su, Z. M.; Xie, Y. Z.; Ding, S. D.; Wang, H. J. Acta Phys. -Chim. Sin. 2011, 27, 2035. [周子彦, 刘敏, 苏忠民, 谢玉忠, 丁慎德, 王华静. 物理化学学报, 2011, 27, 2035.] doi: 10.3866/PKU.WHXB20110903
29. [29]
  (29) Yang, G. H.; Li, Y. X.; Yan, S. H.; Dai, L.; Zhao, B. Acta Chim. Sin. 2011, 69, 1743. [杨国辉, 李言信, 颜世海, 代丽, 赵斌. 化学学报, 2011, 69, 1743.]
30. [30]
  (30) Clavero, C.; Duran, M.; Lledos, A.; Ventura, O. N.; Bertran, J. J. Am. Chem. Soc. 1986, 108, 923. doi: 10.1021/ja00265a014
31. [31]
  (31) Wang, Y.; Zeng, X. L. Acta Phys. -Chim. Sin. 2012, 28, 2831. [王岩, 曾小兰. 物理化学学报, 2012, 28, 2831.] doi: 10.3866/PKU.WHXB201208134
32. [32]
  (32) Hajgató, B.; Takahashi, M.; Kira, M.; Veszprémi, T. Chem. -Eur. J. 2002, 8, 2126. doi: 10.1002/1521-3765(20020503)8:9 <2126::AID-CHEM2126>3.0.CO;2-2
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Mechanism and Regioselectivity of Addition Reactions of CH₃OH to Germasilenes