Citation: LI Wen-Zuo, ZHU Hong-Jie, CHENG Jian-Bo, LI Qing-Zhong, NG Bao-An. Structures of the Triplet Silylenoid HB=SiLiF and Its Insertion Reactions with R—H(R=F, OH, NH₂)[J]. Acta Physico-Chimica Sinica, ;2010, 26(09): 2543-2548. doi: 10.3866/PKU.WHXB20100830 shu

Structures of the Triplet Silylenoid HB=SiLiF and Its Insertion Reactions with R—H(R=F, OH, NH₂)

1.
Chemistry and Biology College, Yantai University, Yantai 264005, Shandong Province, P. R. China

Received Date: 17 March 2010
Available Online: 29 June 2010
Fund Project: 山东省自然科学基金(ZR2009BQ006) (ZR2009BQ006)超分子结构与材料国家重点实验室(吉林大学)开放基金(SKLSSM200909) (吉林大学)开放基金(SKLSSM200909)烟台大学博士科研基金(HY05B30, HY05B36)资助项目 (HY05B30, HY05B36)

Density functional theory (DFT) and quadratic configuration interaction with single and double excitations (QCISD) methods were used to investigate the geometries of the triplet silylenoid HB=SiLiF as well as its insertion reactions with RH (R=F, OH, NH₂). The calculated results indicated that HB=SiLiF has three equilibrium structures wherein the four-membered ring structure had the lowest energy and it was the most stable structure. The mechanisms of the insertion reactions for HB=SiLiF with HF, H₂O, and NH₃ were identical. The QCISD/6-311++G(d,p)//B3LYP/ 6-311+G(d,p) calculated potential energy barriers of the three reactions were 124.85, 140.67, and 148.16 kJ·mol^-1, and the reaction heats for the three reactions were -2.22, 20.08, and 23.22 kJ·mol ^-1, respectively. Under the same conditions, the insertion reactions should occur easily according to the following order: H—F>H—OH>H—NH₂.
- Insertion reaction,
- Silylenoid HB=SiLiF,
- B3LYP,
- QCISD
1. [1]
  
  1. Tamao, K.; Kawachi, A. Angew. Chem. Int. Edit., 1995, 34: 818
2. [2]
  2. Lee, M. E.; Cho, H. M.; Lim, Y. M.; Choi, J. K.; Park, C. H.; Jeong, S. E.; Lee, U. Chem. Eur. J., 2004, 10: 377
3. [3]
  3. Molev, G.; Bravo-Zhivotovakii, D.; Karni, M.; Tumanskii, B.; Botoshansky, M.; Apeloig, Y. J. Am. Chem. Soc., 2006, 128: 2784
4. [4]
  4. Boudjouk, P.; Samaraweera, U. Angew. Chem. Int. Edit., 1988, 27: 1355
5. [5]
  5. Tamao, K.; Kawachi, A. Organometallics, 1995, 14: 3108
6. [6]
  6. Tamao, K.; Kawachi, A. Pure Appl. Chem., 1999, 71: 393
7. [7]
  7. Sekiguchi, A.; Lee, V. Y.; Nanjo, M. Coord. Chem. Rev., 2000, 210: 11
8. [8]
  8. Wiberg, N.; Niedermayer, W. J. Organomet. Chem., 2001, 628: 57
9. [9]
  9. Likhar, P. R.; Zirngast, M.; Baumgartner, J.; Marschner, C. Chem. Commun., 2004: 1764
10. [10]
  10. Kawachi, A.; Oishi, Y.; Kataoka, T.; Tamao, K. Organometallics, 2004, 23: 2949
11. [11]
  11. Lim, Y. M.; Cho, H. M.; Lee, M. E.; Baeck, K. K. Organometallics, 2006, 25: 4960
12. [12]
  12. Harloff, J.; Popowski, E.; Reinke, H. J. Organomet. Chem., 2007, 692: 1421
13. [13]
  13. Clark, T.; Schleyer, P. R. J. Organomet. Chem., 1980, 191: 347
14. [14]
  14. Feng, S.; Feng, D.; Deng, C. Chem. Phys. Lett., 1993, 214: 97
15. [15]
  15. Tanaka, Y.; Kawachi, A.; Hada, M.; Nakatsuji, H.; Tamao, K. Organometallics, 1998, 17: 4573
16. [16]
  16. Feng, S.; Feng, D.; Li, J. Chem. Phys. Lett., 2000, 316: 146
17. [17]
  17. Feng, S.; Feng, D. J. Mol. Struct. -Theochem, 2001, 514: 171
18. [18]
  18. Feng, S.; Feng, D.; Li, M.; Bu, Y. Chem. Phys. Lett., 2001, 339: 103
19. [19]
  19. Feng, S.; Feng, D.; Li, M.; Zhou, Y. Int. J. Quantum Chem., 2002,87: 360
20. [20]
  20. Feng, S.; Zhou, Y.; Feng, D. J. Phys. Chem. A, 2003, 107: 4116
21. [21]
  21. Feng, D.; Xie, J.; Feng, S. Chem. Phys. Lett., 2004, 396: 245
22. [22]
  22. Feng, S.; Lai, G.; Zhou, Y.; Feng, D. Chem. Phys. Lett., 2005, 415: 327
23. [23]
  23. Flock, M.; Marschner, C. Chem. Eur. J., 2005, 11: 4635
24. [24]
  24. Xie, J.; Feng, D.; Feng, S.; Zhang, J. J. Mol. Struct. -Theochem, 2005, 755: 55
25. [25]
  25. Xie, J.; Feng, D.; He, M.; Feng, S. J. Phys. Chem. A, 2005, 109: 10563
26. [26]
  26. Xie, J.; Feng, D.; Feng, S. J. Organomet. Chem., 2006, 691: 208
27. [27]
  27. Xie, J.; Feng, D.; Feng, S. Struct. Chem., 2006, 17: 63
28. [28]
  28. Xie, J.; Feng, D.; Feng, S. J. Comput. Chem., 2006, 27: 933
29. [29]
  29. Xie, J.; Feng, D.; Feng, S.; Zhang, J. Chem. Phys., 2006, 323: 185
30. [30]
  30. Li, W. Z.; ng, B. A.; Cheng, J. B. Acta Phys. -Chim. Sin., 2006, 22: 653 [李文佐,宫宝安, 程建波.物理化学学报, 2006, 22: 653]
31. [31]
  31. Li, W. Z.; ng, B. A.; Cheng, J. B.; Xiao, C. P. Acta Chim. Sin., 2007, 65: 1573 [李文佐,宫宝安,程建波,肖翠平. 化学学报, 2007, 65: 1573]
32. [32]
  32. Xie, J.; Feng, D.; Feng, S.; Ding, Y. Struct. Chem., 2007, 18: 65
33. [33]
  33. Xie, J.; Feng, D.; Feng, S. J. Phys. Chem. A, 2007, 111: 8475
34. [34]
  34. Qi, Y.; Feng, D.; Feng, S. J. Mol. Struct. -Theochem, 2008, 856: 96
35. [35]
  35. Li, W. Z.; Cheng, J. B.; ng, B. A.; Yu, J. K.; Sun, J. Z. Acta Phys. -Chim. Sin., 2008, 24: 901 [李文佐, 程建波,宫宝安, 于健康,孙家钟. 物理化学学报, 2008, 24: 901]
36. [36]
  36. Qi, Y.; Feng, D.; Li, R.; Feng, S. J. Organomet. Chem., 2009, 694: 771
37. [37]
  37. Li, W. Z.; Cheng, J. B.; ng, B. A.; Yu, J. K.; Sun, J. Z. Acta Chim. Sin., 2009, 67: 756 [李文佐,程建波,宫宝安, 于健康, 孙家钟.化学学报, 2009, 67: 756]
38. [38]
  38. Holthausen, M. C.; Koch, W.; Apeloig, Y. J. Am. Chem. Soc., 1999, 121: 2623
39. [39]
  39. Jiang, P.; Gaspar, P. P. J. Am. Chem. Soc., 2001, 123: 8622
40. [40]
  40. Hill, N. J.; West, R. J. Organomet. Chem., 2004, 689: 4165
41. [41]
  41. Cramer, C. J.; Falvey, D. E. Tetrahedron Lett., 1994, 35: 4943
42. [42]
  42. Tachikawa, H.; Yamada, Y.; Lyama, T. Can. J. Chem., 1999, 77: 1419
43. [43]
  43. Gaspar, P. P.; Xiao, M.; Pae, D. H.; Berge, D. J.; Haile, T.; Chen, T.; Lei, D.; Winchester, W. R.; Jiang, P. J. Organomet. Chem., 2002, 646: 68
44. [44]
  44. Yoshida, M.; Tamaoki, N. Organometallics, 2002, 21: 2587
45. [45]
  45. Sekiguchi, A.; Tanaka, T.; Ichinohe, M.; Akiyama, K.; Tero-Kubota S. J. Am. Chem. Soc., 2003, 123: 4962
46. [46]
  46. Xu, Y.; Zhang, Y.; Li, J. J. Phys. Chem. C, 2007, 111: 3729
47. [47]
  47. Skryshevski, Y.; Piryatinski, Y.; Vakhnin, A.; Blonsky, I.; Kadashchuk, A.; Ne?pu觷rek, S. Optical Materials, 2007, 30: 384
48. [48]
  48. Becke, A. D. J. Chem. Phys., 1993, 98: 5648
49. [49]
  49. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B, 1988, 37: 785
50. [50]
  50. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab initio molecular orbital theory. NewYork: Wiley, 1986
51. [51]
  51. nzalez, C.; Schlegel, H. B. J. Phys. Chem., 1991, 95: 5853
52. [52]
  52. Gauss, J.; Cremer, C. Chem. Phys. Lett., 1988, 150: 280
53. [53]
  53. Salter, E. A.; Trucks, G.W.; Bartlett, R. J. J. Chem. Phys., 1989, 90: 1752
54. [54]
  54. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al. Gaussian 03. Revision B.03. Pittsburgh, PA: Gaussian Inc., 2003
55. [55]
  55. Apeloig, Y.; Pauncz, R.; Karni, M.;West, R.; Steiner, W.; Chapman, D. Organometallics, 2003, 22: 3250
1. [1]
  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, 2024, 40(7): 1279-1289. doi: 10.11862/CJIC.20240026
2. [2]
  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, 2024, 40(8): 1511-1518. doi: 10.11862/CJIC.20240072
3. [3]
  Tingbo Wang , Yao Luo , Bingyan Hu , Ruiyuan Liu , Jing Miao , Huizhe Lu . Quantitative Computational Study on the Claisen Rearrangement Reaction of Allyl Phenyl Ethers: An Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(11): 278-285. doi: 10.12461/PKU.DXHX202403082
4. [4]
  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, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
5. [5]
  Zhen Liu , Zhi-Yuan Ren , Chen Yang , Xiangyi Shao , Li Chen , Xin Li . Asymmetric alkenylation reaction of benzoxazinones with diarylethylenes catalyzed by B(C₆F₅)₃/chiral phosphoric acid. Chinese Chemical Letters, 2024, 35(5): 108939-. doi: 10.1016/j.cclet.2023.108939
6. [6]
  Guangchang Yang , Shenglong Yang , Jinlian Yu , Yishun Xie , Chunlei Tan , Feiyan Lai , Qianqian Jin , Hongqiang Wang , Xiaohui Zhang . Regulating local chemical environment in O3-type layered sodium oxides by dual-site Mg²⁺/B³⁺ substitution achieves durable and high-rate cathode. Chinese Chemical Letters, 2024, 35(9): 109722-. doi: 10.1016/j.cclet.2024.109722
7. [7]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
8. [8]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
9. [9]
  Yuting Zhang , Zhiqian Wang . Methods and Case Studies for In-Depth Learning of the Aldol Reaction Based on Its Reversible Nature. University Chemistry, 2024, 39(7): 377-380. doi: 10.3866/PKU.DXHX202311037
10. [10]
  Ruitong Zhang , Zhiqiang Zeng , Xiaoguang Zhang . Improvement of Ethyl Acetate Saponification Reaction and Iodine Clock Reaction Experiments. University Chemistry, 2024, 39(8): 197-203. doi: 10.3866/PKU.DXHX202312004
11. [11]
  Zhenhao Wang , Yuliang Tang , Ruyu Li , Shuai Tian , Yu Tang , Dehai Li . Bioinspired synthesis of cochlearol B and ganocin A. Chinese Chemical Letters, 2024, 35(7): 109247-. doi: 10.1016/j.cclet.2023.109247
12. [12]
  Yuan Chun , Lijun Yang , Jinyue Yang , Wei Gao . Ideological and Political Design of BZ Oscillatory Reaction Experiment. University Chemistry, 2024, 39(2): 72-76. doi: 10.3866/PKU.DXHX202308072
13. [13]
  Shiyan Cheng , Yonghong Ruan , Lei Gong , Yumei Lin . Research Advances in Friedel-Crafts Alkylation Reaction. University Chemistry, 2024, 39(10): 408-415. doi: 10.12461/PKU.DXHX202403024
14. [14]
  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, 2024, 39(3): 359-368. doi: 10.3866/PKU.DXHX202308094
15. [15]
  Shuying Zhu , Shuting Wu , Ou Zheng . Improvement and Expansion of the Experiment for Determining the Rate Constant of the Saponification Reaction of Ethyl Acetate. University Chemistry, 2024, 39(4): 107-113. doi: 10.3866/PKU.DXHX202310117
16. [16]
  Houjin Li , Wenjian Lan . Name Reactions in University Organic Chemistry Laboratory. University Chemistry, 2024, 39(4): 268-279. doi: 10.3866/PKU.DXHX202310016
17. [17]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, 2024, 39(4): 280-285. doi: 10.3866/PKU.DXHX202309001
18. [18]
  Cunling Ye , Xitong Zhao , Hongfang Wang , Zhike Wang . A Formula for the Calculation of Complex Concentrations Arising from Side Reactions and Its Applications. University Chemistry, 2024, 39(4): 382-386. doi: 10.3866/PKU.DXHX202310043
19. [19]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
20. [20]
  Jinyao Du , Xingchao Zang , Ningning Xu , Yongjun Liu , Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039

Get Citation

PDF

XML

Metrics

PDF Downloads(895)
Abstract views(2621)
HTML views(42)

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

Structures of the Triplet Silylenoid HB=SiLiF and Its Insertion Reactions with R—H(R=F, OH, NH2)

Metrics

通讯作者: 陈斌, bchen63@163.com

Structures of the Triplet Silylenoid HB=SiLiF and Its Insertion Reactions with R—H(R=F, OH, NH₂)