三重态类硅烯HB=SiLiF的结构及其与R—H(R=F, OH, NH2)的插入反应

doi:10.3866/PKU.WHXB20100830

Abstract

Abstract:

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.

Key words: Insertion reaction, Silylenoid HB=SiLiF, B3LYP, QCISD

LI Wen-Zuo,ZHU Hong-Jie, CHENG Jian-Bo, LI Qing-Zhong, GONG Bao-An. Structures of the Triplet Silylenoid HB=SiLiF and Its Insertion Reactions with R—H(R=F, OH, NH₂)[J].Acta Phys. -Chim. Sin., 2010, 26(09): 2543-2548.

References

1. Tamao, K.; Kawachi, A. Angew. Chem. Int. Edit., 1995, 34: 818
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. Molev, G.; Bravo-Zhivotovakii, D.; Karni, M.; Tumanskii, B.; Botoshansky, M.; Apeloig, Y. J. Am. Chem. Soc., 2006, 128: 2784
4. Boudjouk, P.; Samaraweera, U. Angew. Chem. Int. Edit., 1988, 27: 1355
5. Tamao, K.; Kawachi, A. Organometallics, 1995, 14: 3108
6. Tamao, K.; Kawachi, A. Pure Appl. Chem., 1999, 71: 393
7. Sekiguchi, A.; Lee, V. Y.; Nanjo, M. Coord. Chem. Rev., 2000, 210: 11
8. Wiberg, N.; Niedermayer, W. J. Organomet. Chem., 2001, 628: 57
9. Likhar, P. R.; Zirngast, M.; Baumgartner, J.; Marschner, C. Chem. Commun., 2004: 1764
10. Kawachi, A.; Oishi, Y.; Kataoka, T.; Tamao, K. Organometallics, 2004, 23: 2949
11. Lim, Y. M.; Cho, H. M.; Lee, M. E.; Baeck, K. K. Organometallics, 2006, 25: 4960
12. Harloff, J.; Popowski, E.; Reinke, H. J. Organomet. Chem., 2007, 692: 1421
13. Clark, T.; Schleyer, P. R. J. Organomet. Chem., 1980, 191: 347
14. Feng, S.; Feng, D.; Deng, C. Chem. Phys. Lett., 1993, 214: 97
15. Tanaka, Y.; Kawachi, A.; Hada, M.; Nakatsuji, H.; Tamao, K. Organometallics, 1998, 17: 4573
16. Feng, S.; Feng, D.; Li, J. Chem. Phys. Lett., 2000, 316: 146
17. Feng, S.; Feng, D. J. Mol. Struct. -Theochem, 2001, 514: 171
18. Feng, S.; Feng, D.; Li, M.; Bu, Y. Chem. Phys. Lett., 2001, 339: 103
19. Feng, S.; Feng, D.; Li, M.; Zhou, Y. Int. J. Quantum Chem., 2002,87: 360
20. Feng, S.; Zhou, Y.; Feng, D. J. Phys. Chem. A, 2003, 107: 4116
21. Feng, D.; Xie, J.; Feng, S. Chem. Phys. Lett., 2004, 396: 245
22. Feng, S.; Lai, G.; Zhou, Y.; Feng, D. Chem. Phys. Lett., 2005, 415: 327
23. Flock, M.; Marschner, C. Chem. Eur. J., 2005, 11: 4635
24. Xie, J.; Feng, D.; Feng, S.; Zhang, J. J. Mol. Struct. -Theochem, 2005, 755: 55
25. Xie, J.; Feng, D.; He, M.; Feng, S. J. Phys. Chem. A, 2005, 109: 10563
26. Xie, J.; Feng, D.; Feng, S. J. Organomet. Chem., 2006, 691: 208
27. Xie, J.; Feng, D.; Feng, S. Struct. Chem., 2006, 17: 63
28. Xie, J.; Feng, D.; Feng, S. J. Comput. Chem., 2006, 27: 933
29. Xie, J.; Feng, D.; Feng, S.; Zhang, J. Chem. Phys., 2006, 323: 185
30. Li, W. Z.; Gong, 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. Li, W. Z.; Gong, 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. Xie, J.; Feng, D.; Feng, S.; Ding, Y. Struct. Chem., 2007, 18: 65
33. Xie, J.; Feng, D.; Feng, S. J. Phys. Chem. A, 2007, 111: 8475
34. Qi, Y.; Feng, D.; Feng, S. J. Mol. Struct. -Theochem, 2008, 856: 96
35. Li, W. Z.; Cheng, J. B.; Gong, 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. Qi, Y.; Feng, D.; Li, R.; Feng, S. J. Organomet. Chem., 2009, 694: 771
37. Li, W. Z.; Cheng, J. B.; Gong, 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. Holthausen, M. C.; Koch, W.; Apeloig, Y. J. Am. Chem. Soc., 1999, 121: 2623
39. Jiang, P.; Gaspar, P. P. J. Am. Chem. Soc., 2001, 123: 8622
40. Hill, N. J.; West, R. J. Organomet. Chem., 2004, 689: 4165
41. Cramer, C. J.; Falvey, D. E. Tetrahedron Lett., 1994, 35: 4943
42. Tachikawa, H.; Yamada, Y.; Lyama, T. Can. J. Chem., 1999, 77: 1419
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. Yoshida, M.; Tamaoki, N. Organometallics, 2002, 21: 2587
45. Sekiguchi, A.; Tanaka, T.; Ichinohe, M.; Akiyama, K.; Tero-Kubota S. J. Am. Chem. Soc., 2003, 123: 4962
46. Xu, Y.; Zhang, Y.; Li, J. J. Phys. Chem. C, 2007, 111: 3729
47. Skryshevski, Y.; Piryatinski, Y.; Vakhnin, A.; Blonsky, I.; Kadashchuk, A.; Ne?pu觷rek, S. Optical Materials, 2007, 30: 384
48. Becke, A. D. J. Chem. Phys., 1993, 98: 5648
49. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B, 1988, 37: 785
50. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab initio molecular orbital theory. NewYork: Wiley, 1986
51. Gonzalez, C.; Schlegel, H. B. J. Phys. Chem., 1991, 95: 5853
52. Gauss, J.; Cremer, C. Chem. Phys. Lett., 1988, 150: 280
53. Salter, E. A.; Trucks, G.W.; Bartlett, R. J. J. Chem. Phys., 1989, 90: 1752
54. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al. Gaussian 03. Revision B.03. Pittsburgh, PA: Gaussian Inc., 2003
55. Apeloig, Y.; Pauncz, R.; Karni, M.;West, R.; Steiner, W.; Chapman, D. Organometallics, 2003, 22: 3250

[1]	YANG Shu, YANG Xiao-Mei, XIE Xiao-Guang. Theoretical Study of Gas-Phase Reaction of YS⁺ (¹Σ⁺, ³Φ) with COS: YS⁺+COS→YS₂⁺+CO [J]. Acta Phys. -Chim. Sin., 2012, 28(08): 1892-1898.
[2]	FENG Li-Xia, JIN Ling-Xia, WANG Wei-Na, WANG Wen-Liang. Mechanism and Kinetics of the Hydrogen Abstraction Reaction of C₂H₃ with CH₃F [J]. Acta Phys. -Chim. Sin., 2012, 28(07): 1623-1629.
[3]	LIU Hai-Ying, MENG Fan-Cui, LI Ping, DING Shi-Liang. Effects of CH₃OH and NH₃ on the Hydrolytic Deamination Mechanismof Adenine [J]. Acta Phys. -Chim. Sin., 2010, 26(11): 3067-3072.
[4]	SUN Long, XIE Ju. Insertion Reactions of Heterocyclic Stable Silylenes into HF, H₂O and NH₃ [J]. Acta Phys. -Chim. Sin., 2010, 26(05): 1429-1434.
[5]	ZHANG Jia-Hu, WANG Xiu-Jun. Neural Network Approach for a New B3LYP Functional with an Enlarged Training Set [J]. Acta Phys. -Chim. Sin., 2010, 26(01): 188-192.
[6]	FARMANZADEH Davood, AMIRAZAMI Abolfazl. Electric Field Dependence of (4, 0) Zigzag Model Single-Walled Carbon Nanotube [J]. Acta Phys. -Chim. Sin., 2009, 25(11): 2343-2349.
[7]	LIU Yan-Zhu, ZHANG Ling, LI Xia, LI Yong-Xiu. Comparison among the Spectral Properties ofMethyl Salicylate and Its Nitration Products by Iron (III) Nitrate [J]. Acta Phys. -Chim. Sin., 2009, 25(10): 2118-2122.
[8]	CAO Yu-Cai, LI You. Dearsenication of Liquid Hydrocarbons and Interaction between Arsenic Compounds and Cuprous Probes [J]. Acta Phys. -Chim. Sin., 2009, 25(08): 1495-1503.
[9]	LI Wen-Zuo; CHENG Jian-Bo; LI Qing-Zhong; GONG Bao-An; SUN Jia-Zhong. Structures and Isomerization Reactions of the Germylenoid H₂GeClMgCl in Solution [J]. Acta Phys. -Chim. Sin., 2009, 25(01): 121-125.
[10]	LI Wen-Zuo; CHENG Jian-Bo; GONG Bao-An; YU Jian-Kang; SUN Jia-Zhong. Structures and Isomerization Reactions of the Silylenoid H₂SiClBeCl [J]. Acta Phys. -Chim. Sin., 2008, 24(05): 901-904.
[11]	LI Wen-Zuo; XIAO Cui-Ping; GONG Bao-An; CHENG Jian-Bo. Insertion Reactions of the Germylenoid H₂C=GeLiCl with RH(R=F, OH, NH₂) [J]. Acta Phys. -Chim. Sin., 2008, 24(04): 720-724.
[12]	CHEN Si-Cong; WANG Yu; CHEN Jue-Xiao; TENG Qi-Wen. Electronic Structures and Fluorescent Spectra of 1,4-divinylphenyl-bridged Triphenylenes [J]. Acta Phys. -Chim. Sin., 2008, 24(02): 187-192.
[13]	ZHANG Cheng-Gen;LI Wen-Zuo;HUANG Ming-Bao. Reaction of Methyl Alcohol with Thionyl Chloride in Solution [J]. Acta Phys. -Chim. Sin., 2007, 23(03): 399-403.
[14]	MENG Xiang-jun. Theoretical Study on Structures and Properties of Dihydrated Zwitterionic Glycine Complexes [J]. Acta Phys. -Chim. Sin., 2006, 22(01): 98-101.
[15]	Han Xiang-Yun;Wang Zun-Yao;Wang Lian-Sheng;Yang Chun-Sheng;Yu Bin. Kinetics of Synthetic of Cl－ Type Hydrotalcitelike with Coprecipitation Reaction [J]. Acta Phys. -Chim. Sin., 2004, 20(11): 1364-1368.

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

PDF

Like

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Metrics

Comments

Recommended 0

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

PDF

Like

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Metrics

Comments

Recommended 0

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