Citation: WANG Yan, ZENG Xiao-Lan. 1,2- and 1,4-Addition Reactions between Silabenzenes and HX (X=F, OH, NH₂)[J]. Acta Physico-Chimica Sinica doi: 10.3866/PKU.WHXB201208134 shu

1,2- and 1,4-Addition Reactions between Silabenzenes and HX (X=F, OH, NH₂)

WANG Yan ,
ZENG Xiao-Lan

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

Received Date: 20 June 2012
Available Online: 13 August 2012
Fund Project: 河南省基础与前沿技术研究计划(092300410207)资助项目 (092300410207)

Density functional theory calculations at the B3LYP/6-311 ++ G(d,p) level were performed to study the reaction mechanism and potential energy surface of the 1,2- and 1,4-addition reactions between silabenzenes and HX (X=F, OH, NH₂). The influences of substituents at the Si atom and tetrahydrofuran as a solvent on the potential energy surfaces of the reactions were also explored. The results indicated that the title reactions occur by the following two mechanisms: (1) silabenzene and one HX molecule form an intermediate complex, and then isomerize to give final product via a four-membered transition state; and (2) silabenzene and two HX molecules form an intermediate complex, and then isomerize via a sixmembered transition state to give another intermediate complex from which one HX molecule is left to afford the final product. Mechanism 2 is much more favorable than mechanism 1 kinetically. The preference for the 1,2- or 1,4-addition product is determined by kinetics and is related to the X group. The reactivity order of HX toward the addition reaction with silabenzene in gas phase is HF>H₂O>NH₃. Strong electron-donating and -withdrawing substituents at the Si atom have a favorable influence on the potential energy surfaces of the 1,2- and 1,4-addition reactions, while the large mesityl group has the opposite effect. Tetrahydrofuran has an unfavorable thermodynamic influence on the reactions, and kinetically on those reactions with HF or H₂O. However, it favors the reactions between silabenzenes and NH3 kinetically.
- Density functional theory,
- Silabenzene,
- Addition reaction,
- Reaction mechanism
1. [1]
  
  (1) Barton, T. J.; Burns, G. T. J. Am. Chem. Soc. 1978, 100, 5246.doi: 10.1021/ja00484a075
2. [2]
  (2) Ando,W.; Tanikawa, H.; Sekiguchi, A. Tetrahedron Lett. 1983,24, 4245. doi: 10.1016/S0040-4039(00)88312-4
3. [3]
  (3) Kreil, C. L.; Chapman, O. L.; Burns, G. T.; Barton, T. J. J. Am. Chem. Soc. 1980, 102, 841. doi: 10.1021/ja00522a068
4. [4]
  (4) Barton, T. J.; Vuper, M. J. Am. Chem. Soc. 1981, 103, 6788.doi: 10.1021/ja00412a061
5. [5]
  (5) Märkl, G.; Hofmeister, P. Angew. Chem. Int. Edit. 1979, 18,789.
6. [6]
  (6) Wakita, K.; Tokitoh, N.; Okazaki, R.; Takagi, N.; Nagase, S.J. Am. Chem. Soc. 2000, 122, 5648. doi: 10.1021/ja000309i
7. [7]
  (7) Wakita, K.; Tokitoh, N.; Okazaki, R.; Nagase, S. Angew. Chem. Int. Edit. 2000, 39, 634.
8. [8]
  (8) Tokitoh, N. Accounts Chem. Res. 2004, 37, 86. doi: 10.1021/ar020093k
9. [9]
  (9) Schlegel, H. B.; Coleman, B.; Jones, M. J. Am. Chem. Soc.1978, 100, 6499. doi: 10.1021/ja00488a039
10. [10]
  (10) Blustin, P. H. J. Organomet. Chem. 1979, 166, 21. doi: 10.1016/S0022-328X(00)91416-5
11. [11]
  (11) Reyes, L. M.; Canuto, S. J. Mol. Struct. -Theochem 1982, 89,77. doi: 10.1016/0166-1280(82)80154-1
12. [12]
  (12) Chandrasekhar, J.; Schleyer, P. v. R.; Baumgaertner, R. O.W.;Reetz, M. T. J. Org. Chem. 1983, 48, 3453.
13. [13]
  (13) Baldridge, K. K.; rdon, M. S. Organometallics 1988, 7, 144.doi: 10.1021/om00091a023
14. [14]
  (14) Baldridge, K. K.; Uzan, O.; Martin, J. M. L. Organometallics2000, 19, 1477. doi: 10.1021/om9903745
15. [15]
  (15) Priyakumar, U. D.; Sastry, G. N. Organometallics 2002, 21,1493. doi: 10.1021/om011001i
16. [16]
  (16) Dhevi, D. M.; Priyakumar, U. D.; Sastry, G. N. J. Mol. Struct. -Theochem 2002, 618, 173. doi: 10.1016/S0166-1280(02)00470-0
17. [17]
  (17) Santos, J. C.; Fuentealba, P. Chem. Phys. Lett. 2007, 443, 439.doi: 10.1016/j.cplett.2007.06.105
18. [18]
  (18) Shinohara, A.; Takeda, N.; Sasamori, T.; Matsumoto, T.;Tokitoh, N. Organometallics 2005, 24, 6141. doi: 10.1021/om0501778
19. [19]
  (19) Zhang, S. G.; Liu, J. H.; Zhang,W. X.; Xi, Z. F. Prog. Chem.2009, 21, 1487. [张韶光, 刘俊辉, 张文雄, 席振峰. 化学进展, 2009, 21, 1487.]
20. [20]
  (20) Wang, Y.; Zeng, X. L.;Wang, L. Acta Phys. -Chim. Sin. 2009,25, 371. [王岩, 曾小兰, 汪玲. 物理化学学报, 2009, 25,371.] doi: 10.3866/PKU.WHXB20090230
21. [21]
  (21) Wang, Y.; Zeng, X. L.; Fang, D. C. Acta Chim. Sin. 2010, 68,941. [王岩, 曾小兰, 方德彩. 化学学报, 2010, 68, 941.]
22. [22]
  (22) Li, B. Y.; Sheu, J. H.; Su, M. D. Organometallics 2011, 30, 4862.
23. [23]
  (23) Li, B. Y.; Su, M. D. Organometallics 2011, 30, 6189.doi: 10.1021/om200725u
24. [24]
  (24) Cossi, M.; Barone, V.; Cammi, R.; Tomasi, J. Chem. Phys. Lett.1996, 255, 327. doi: 10.1016/0009-2614(96)00349-1
25. [25]
  (25) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03,Revision B.02; Gaussian Inc.: Pittsburgh, PA, 2003.
26. [26]
  (26) Bader, R. F.W. Chem. Rev. 1991, 91, 893. doi: 10.1021/cr00005a013
27. [27]
  (27) Biegler-Konig, F.; Schonbohm, J. J. Comput. Chem. 2002, 23,1489.
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.]
1. [1]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, doi: 10.3866/PKU.DXHX202309101
2. [2]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, doi: 10.3866/PKU.DXHX202310095
3. [3]
  Ling Fan , Meili Pang , Yeyun Zhang , Yanmei Wang , Zhenfeng Shang . Quantum Chemistry Calculation Research on the Diels-Alder Reaction of Anthracene and Maleic Anhydride: Introduction to a Computational Chemistry Experiment. University Chemistry, doi: 10.3866/PKU.DXHX202309024
4. [4]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, doi: 10.3866/PKU.DXHX202309001
5. [5]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20230385
6. [6]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240078
7. [7]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, doi: 10.3866/PKU.DXHX202310047
8. [8]
  Xingyang LI , Tianju LIU , Yang GAO , Dandan ZHANG , Yong ZHOU , Meng PAN . A superior methanol-to-propylene catalyst: Construction via synergistic regulation of pore structure and acidic property of high-silica ZSM-5 zeolite. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240026
9. [9]
  Jiaqi AN , Yunle LIU , Jianxuan SHANG , Yan GUO , Ce LIU , Fanlong ZENG , Anyang LI , Wenyuan WANG . Reactivity of extremely bulky silylaminogermylene chloride and bonding analysis of a cubic tetragermylene. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240072
10. [10]
  Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, doi: 10.3866/PKU.DXHX202312006
11. [11]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240007
12. [12]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB202311026
13. [13]
  Qian Huang , Zhaowei Li , Jianing Zhao , Ao Yu . Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon. University Chemistry, doi: 10.3866/PKU.DXHX202309018
14. [14]
  Yong Wang , Yingying Zhao , Boshun Wan . Analysis of Organic Questions in the 37th Chinese Chemistry Olympiad (Preliminary). University Chemistry, doi: 10.12461/PKU.DXHX202403009
15. [15]
  Yiying Yang , Dongju Zhang . Elucidating the Concepts of Thermodynamic Control and Kinetic Control in Chemical Reactions through Theoretical Chemistry Calculations: A Computational Chemistry Experiment on the Diels-Alder Reaction. University Chemistry, doi: 10.3866/PKU.DXHX202309074
16. [16]
  Yuting Zhang , Zhiqian Wang . Methods and Case Studies for In-Depth Learning of the Aldol Reaction Based on Its Reversible Nature. University Chemistry, doi: 10.3866/PKU.DXHX202311037
17. [17]
  Ruitong Zhang , Zhiqiang Zeng , Xiaoguang Zhang . Improvement of Ethyl Acetate Saponification Reaction and Iodine Clock Reaction Experiments. University Chemistry, doi: 10.3866/PKU.DXHX202312004
18. [18]
  Yuan Chun , Lijun Yang , Jinyue Yang , Wei Gao . Ideological and Political Design of BZ Oscillatory Reaction Experiment. University Chemistry, doi: 10.3866/PKU.DXHX202308072
19. [19]
  Shiyan Cheng , Yonghong Ruan , Lei Gong , Yumei Lin . Research Advances in Friedel-Crafts Alkylation Reaction. University Chemistry, doi: 10.12461/PKU.DXHX202403024
20. [20]
  Feiya Cao , Qixin Wang , Pu Li , Zhirong Xing , Ziyu Song , Heng Zhang , Zhibin Zhou , Wenfang Feng . Magnesium-Ion Conducting Electrolyte Based on Grignard Reaction: Synthesis and Properties. University Chemistry, doi: 10.3866/PKU.DXHX202308094

Get Citation

PDF

XML

Metrics

PDF Downloads(640)
Abstract views(2306)
HTML views(3)

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

1,2- and 1,4-Addition Reactions between Silabenzenes and HX (X=F, OH, NH2)

Metrics

通讯作者: 陈斌, bchen63@163.com

1,2- and 1,4-Addition Reactions between Silabenzenes and HX (X=F, OH, NH₂)