Density Functional Study on the C-H Bond Cleavage of Aldimine by a Rhodium(I) Catalyst

다국어 초록 (Multilingual Abstract)

We investigated the C-H bond activation mechanism of aldimine by the [RhCl(PPH3)3] model catalyst using
DFT B3LYP//SBKJC/6-31G*/6-31G on GAMESS. Due to their potential utility in organic synthesis, C-H
bond activation is one of the most active research fields in organic and organometallic chemistry. C-H bond
activation by a transition metal catalyst can be classified into two types of mechanisms: direct C-H bond
cleavage by the metal catalyst or a multi-step mechanism via a tetrahedral transition state. There are three
structural isomers of [RhCl(PH3)2] coordinated aldimine that differ in the position of chloride with respect to
the molecular plane. By comparing activation energies of the overall reaction pathways that the three isomeric
structures follow in each mechanism, we found that the C-H bond activation of aldimine by the [RhCl(PH3)3]
catalyst occurs through the tetrahedral intermediate.

참고문헌 (Reference)

1 Arndtsen, B. A, 28 : 154-, 1995

2 Bennet, M. J, 16 : 655-, 1977

3 Shilov, A. E, 97 : 2879-, 1997

4 Dyker, G., 38 : 1698-, 1999

5 Kakiuchi, F, 35 : 826-, 2002

6 Kakiuchi, F, 345 : 1077-, 2003

7 Kondo, T, 55 : 1286-, 1990

8 Lenges, C. P, 120 : 6965-, 1998

9 Kondo, T, 17 : 2131-, 1998

10 Tanaka, M, 5 : 1365-, 2003

11 Kokubo, K, 62 : 4564-, 1997

12 Jun, C.-H, 62 : 1200-, 1997

13 Jun, C.-H., 37 : 145-, 1998

14 Jun, C.-H, 1 : 887-, 1999

15 Jun, C.-H, 41 : 2146-, 2002

16 Jun, C.-H, 39 : 3070-, 2000

17 Jun, C.-H, 8 : 2422-, 2002

18 Jun, C.-H, 41 : 2146-2147, 2002

19 Park, Y. J, 126 : 13892-13893, 2004

20 Jo, E.-A, 2504-2507, 2006

21 Suggs, J. W, 101 : 489-, 1979

22 Heiberg, H, 92 : 391-, 2003

23 Broclawik, E, 2001 : 333-332, 2001

24 Wiedemann, S. H, 128 : 2452-, 2006

25 Yoshizawa, K, 17 : 2825-, 1998

26 Jazzar, R. F. R, 359 : 815-, 2006

27 Crabtree, R. H, 85 : 245-, 1985

28 Markies, B. A, 1420-, 1992

29 Gozin, M, 364 : 600-, 1993

30 van der Boom, M. E, 103 : 1759-, 2003

31 Vigalok, A, 34 : 798-, 2001

32 Stevens, W. J, 81 : 6026-, 1984

33 Stevens, W. J, 70 : 612-, 1992

34 Cundari, T. R, 98 : 5555-, 1993

35 Schmidt, M. W, 14 : 1347-, 1993

36 Musaev, D. G, 116 : 10693-, 1994

37 Dorigo, A. E, 34 : 115-, 1995

38 Widauer, C, 19 : 2097-, 2000

39 Liu, D, 21 : 4750-, 2002

40 Cui, Q, 16 : 1355-, 1997

41 Cui, Q, 17 : 742-, 1998

42 Matsubara, T, 100 : 2573-, 1996

43 Sumimoto, M, 126 : 10457-, 2004

44 Lam, W. H, 1556-, 2004

45 Tamura, H, 125 : 16114-, 2003

46 Niu, S, 100 : 353-, 2000