Computational Studies on the Reaction from Silyl 1,4-Dilithio 1,3-butadiene to Lithio Silole

다국어 초록 (Multilingual Abstract)

The reaction mechanisms forming lithio silole, 2, from silyl 1,4-dilithio 1,3-butadiene, 1, were examined theoretically at the CCSD/6-31+G(d)//B3LYP/6-31+G(d) level of theory in the gas phase. To account for the solvent effects, the reactions in diethyl ether were examined using the polarizable continuum model of the integral equation formalism (IEFPCM) with the united atom topological (UA0) cavity model at the IEFPCM-CCSD/6-31+G(d)//IEFPCM-B3LYP/6-31+G(d) level of theory. Without hexamethyl-phosphoramide (HMPA) as a cosolvent, the lithio silole, 2, was not produced due to the higher activation barrier, which is comparable to the homolytic cleavage of CC and/or CS bonds. On the other hand, the reaction could be feasible if HMPA solvates strongly or dissociates two Li+ cations from the reaction system. This suggests that HMPA plays a decisive role in the reaction. The optimized structures of the stationary point species on the potential energy surfaces in diethyl ether were similar to those in the gas phase, suggesting that the solvent effects on the structures of stationary species were not so large. On the other hand, theΔ E ZPVE ≠ values in diethyl ether showed larger changes from the corresponding values in the gas phase.

참고문헌 (Reference)

1 V. N. Vandyshev, 169 : 57-, 1990

2 J. Tomasi, 464 : 211-, 1999

3 F. Birkeneder, 583 : 152-, 1990

4 J. Rannou, 324-, 1989

5 M. Castagnolo, 79 : 2211-, 1983

6 W. R. Gilkerson, 101 : 4096-, 1979

7 P. Goralski, 86 : 3103-, 1990

8 B. Mennucci, 101 : 10506-, 1997

9 B. Mennucci, 106 : 5151-, 1997

10 M. T. Cancès, 107 : 3032-, 1997

11 S. Al-Rusaese, 110 : 8676-, 2006

12 M. A. Beswick, 18 : 1148-, 1999

13 M. Cossi, 255 : 327-, 1996

14 A. J. Kos, 102 : 7928-, 1980

15 A. J. Ashe III., 10 : 2424-, 1991

16 U. Schubert, 1184-, 1982

17 W. Bauer, 110 : 6033-, 1988

18 A. J. Ashe III., 12 : 3350-, 1993

19 L. Liu, 29 : 278-, 2010

20 F. Pauer, 474 : 27-, 1994

21 M. Saito, 46 : 1504-, 2007

22 E. Negishi, 108 : 3402-, 1986

23 E. H. Braye, 1250-, 1959

24 J. Dubac, 90 : 215-, 1990

25 E. Colomer, 90 : 265-, 1990

26 D. H. O’Brien, 103 : 3237-, 1981

27 E. G. Janzen, 10 : 6-, 1967

28 S. Yamaguchi, 69 : 2327-, 1996

29 K. Tamao, 68 : 139-, 1996

30 K. Tamao, 118 : 11947-, 1996

31 S. Yamaguchi, 78 : 721-, 2006

32 S. Yamaguchi, 63 : 1115-, 2005

33 S. Yamaguchi, 653 : 223-, 2002

34 S. Yamaguchi, 6 : 1683-, 2000

35 S. Yamaguchi, 121 : 10420-, 1999

36 S. Yamaguchi, 3693-, 1998

37 K. Tamao, 116 : 11715-, 1994

38 C. Wang, 129 : 3094-, 2007

39 M. Murakami, 78 : 415-, 2006

40 G. Zweifel, 46 : 1292-, 1981

41 R. Knorr, 23 : 366-, 1984

42 F. Sato, 1126-, 1982

43 E. Negishi, 105 : 6761-, 1983

44 G. A. Molander, 48 : 5409-, 1983

45 J. A. Miller, 24 : 76-, 1984

46 T. Yoshida, 103 : 1276-, 1981

47 P. von Ragué Schleyer, 56 : 151-, 1984

48 E. Negishi, 105 : 6344-, 1983

49 L. D. Boardman, 106 : 6105-, 1984

50 Z. Wang, 46 : 499-, 2005

51 P. F. Hudrlik, 691 : 1257-, 2006

52 T. L. Cottrell, "The Strengths of Chemical Bonds" Butterworths Scientific Publications 1958

53 M. J. Frisch, "Gaussian 03, Revision C.02"

54 J. L. Wardell, "Comprehensive Organometallic Chemistry, Vol. 1" Pergamon 1982

55 J. March, "Advanced Organic Chemistry" John Wiley &Sons 77-, 1985