Observation of the Hammick intermediate: Reduction of the pyridine-2-ylid ion in the gas phase

Journal of the American Chemical Society

Volumn 118, Issue 47, 1996, Pages 11898-11904

  Lavorato, David ^a   Terlouw, Johan K ^a   Dargel, Thomas K ^b   Koch, Wolfram ^b   McGibbon, Graham A ^b,c   Schwarz, Helmut ^b  

^a MCMASTER UNIVERSITY   (Canada)

^b TECHNISCHE UNIVERSITÄT BERLIN   (Germany)

^c UNIVERSITY OF WATERLOO   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

PYRIDINE;

ARTICLE; DRUG STRUCTURE; IONIZATION; MOLECULAR DYNAMICS; THEORY; THERMODYNAMICS;

EID: 0029960585     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961954l     Document Type: Article

References (82)

1. Nef, J. U. Liebigs Ann. Chem. 1895, 287, 359.
2. (a) Wentrup, C. Reaktive Zwischenstufen; Georg Thieme Verlag: Stuttgart, 1979.
3. (b) Kirmse, W. Carbene Chemistry, 2nd ed.; Academic Press: New York, 1971.
4. Moss, R. A. Acc. Chem. Res. 1989, 22, 15.
5. (a) Arduengo III, A. J.; Gamper, S. F.; Tamm, M.; Calabrese, J. C.; Davidson, F.; Craig, H. A. J. Am. Chem. Soc. 1995, 117, 572.
6. (b) Arduengo III, A. J.; Dixon, D. A.; Kumashiro, K. K.; Lee, C.; Power, W. P.; Zilm, K. W. J. Am. Chem. Soc. 1994, 116, 6361.
7. (c) Arduengo III, A. J.; Dias, H. V. R., Dixon, D. A.; Harlow, R. L.; Klooster, W. T.; Koetzle, T. F. J. Am. Chem. Soc. 1994, 116, 6812.
8. For two very recent reports, see: (a) Ghosh, A. Angew. Chem. 1995, 107, 1117. (b) Enders, D.; Breuer, K.; Raabe, G.; Runsink, J.; Teles, J. H.; Melder, J.-P.; Ebel, K.; Brode, S. Angew. Chem. 1995, 107, 1119.
9. For two very recent reports, see: (a) Ghosh, A. Angew. Chem. 1995, 107, 1117. (b) Enders, D.; Breuer, K.; Raabe, G.; Runsink, J.; Teles, J. H.; Melder, J.-P.; Ebel, K.; Brode, S. Angew. Chem. 1995, 107, 1119.
10. Wanzlick, H.-W. Angew. Chem. 1962, 74, 129.
11. Jones, W. M.; Ennis, C. L. J. Am. Chem. Soc. 1967, 89, 3069.
12. Gleiter, R.; Hoffman, R. J. Am. Chem. Soc. 1968, 90, 5457.
13. (a) Dyson, P.; Hammick, D. L. J. Chem. Soc. 1937, 1724.
14. (b) Ashworth, M. R. F.; Daffern, R, P.; Hammick, D. L. J. Chem. Soc. 1937, 809.
15. (a) Quast, H.; Frankenfeld, E. Angew. Chem. 1965, 77, 680.
16. (b) Haake, P.; Mantecon, J. J. Am. Chem. Soc. 1964, 86, 5230.
17. Bonn, B.; Heinrich, N.; Vorbrüggen H. Heterocycles 1994, 37, 1731.
18. Breslow, R. J. Am. Chem. Soc. 1958, 80, 3719.
19. (a) Dixon, D. A.; Arduengo III, A. J. J. Phys. Chem. 1991, 95, 4180.
20. (b) Alder, R. W.; Alien, P. R.; Williams, S. J. J. Chem. Soc., Chem. Commun. 1995, 1267.
21. (c) Cioslowski, J. Int. J. Quant. Chem., Quant. Chem. Symp. 1993, 27, 309.
22. (a) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwarz, H. J. Am. Chem. Soc. 1996, 118, 2023.
23. (b) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039.
24. (c) Arduengo III, A. J.; Bock, H.; Chen, H.; Denk, M.; Dixon, D. A.; Green, J. C.; Herrmann, W. A.; Jones, N. L.; Wagner, M.; West, R. J. Am. Chem. Soc. 1994, 116, 6641.
25. (d) Heinemann, C.; Thiel, W. Chem. Phys. Lett. 1994, 217, 11.
26. (a) Wanzlick, H.-W.; Schikora, E. Angew. Chem. 1960, 72, 494.
27. (b) Wanzlick, H.-W. Angew. Chem. 1962, 74, 129.
28. (c) Lemal, D. M.; Kawano, K. I. J. Am. Chem. Soc. 1962, 84, 1761.
29. (d) Lemal, D. M.; Lovald, R. A.; Kawano, K. I. J. Am. Chem. Soc. 1964, 86, 2518.
30. (e) Schönherr, H. J. Ph.D. Thesis, Technische Universität Berlin, D83, 1970.
31. (f) Schönherr, H. J.; Wanzlick, H.-W. Chem. Ber. 1970, 103, 1037.
32. (a) Denk, M.; Green, J. C.; Metzler, N.; Wagner, M. J. Chem. Soc., Dalton Trans: 1994, 2405.
33. (b) Denk, M.; Lennon, R.; Hayashi, R.; West, R.; Belyakov, A. V.; Verne, H. P.; Haaland, A.; Wagner, M.; Metzler, N. J. Am. Chem. Soc. 1994, 116, 2691.
34. Igau, A.; Grützmacher, H.; Baceiredo, A.; Bertrand, G. J. Am. Chem. Soc. 1988, 110, 6463.
35. Recent reviews: (a) Goldberg, N.; Schwarz, H. Acc. Chem. Res. 1994, 27, 347. (b) McLafferty, F. W. Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 211.
36. Recent reviews: (a) Goldberg, N.; Schwarz, H. Acc. Chem. Res. 1994, 27, 347. (b) McLafferty, F. W. Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 211.
37. McGibbon, G. A.; Kingsmill, C. A.; Terlouw, J. K. Chem. Phys. Lett. 1994, 222, 129.
38. (a) McGibbon, G. A.; Burgers, P. C.; Terlouw, J. K. Int. J. Mass Spectrom. Ion Processes 1994, 136, 191.
39. (b) Hop, C. E. C. A.; Chen, H.; Ruttink, P. J. A.; Holmes, J. L. Org. Mass Spectrom. 1991, 26, 697.
40. (c) Schaftenaar, G.; Postma, R.; Ruttink, P. J. A.; Burgers. P. C.; McGibbon, G. A.; Terlouw, J. K. Int. J. Mass Spectrom. Ion Processes 1990, 100, 521.
41. Wesdemiotis, C.; McLafferty, F. W. J. Am. Chem. Soc. 1987, 109, 4760.
42. Sülzle, D.; Drewello, T.; van Baar, B. L. M.; Schwarz, H. J. Am. Chem. Soc. 1988, 110, 8330.
43. (a) Feng, R.; Wesdemiotis, C.; McLafferty, F. W. J. Am. Chem. Soc. 1987, 109, 6521.
44. (b) Bouma, W. J.; Burgers, P. C: Holmes, J. L.; Radom, L. J. Am. Chem. Soc. 1986, 108, 1767.
45. Goldberg, N.; Fiedler, A.; Schwarz, H. Helv. Chem. Acta 1994, 77, 2354.
46. Goldberg, N.; Iraqi, M.; Schwarz, H. Chem. Ber. 1993, 126, 2353.
47. Chen. P. H. J. Org. Chem. 1976. 41, 2973.
48. Grigg, R.; Wallace, L.; Morley, J. O. J. Chem. Soc., Perkin Trans. 2 1990, 51.
49. Nyulaszi, L.; Szieberth. D.; Veszpremi, T. 8th International Congress of Quantum Chemistry; Prague, June 19-23 1994.
50. Gaussian 94 (Revision B.3); Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb. M. A.; Cheeseman, J. R.; Keith, T. A.; Petersson, G. A.; Montgomery, J. A.; Raghavachari. K.; AlLaham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley. J. S.; DeFrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C; Pople, J. A. Gaussian, Inc.: Pittsburgh, PA, 1995.
51. For a competent review on these techniques, see: Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley Interscience: New York, 1986.
52. Chen, W.; Schlegel, H. B. J. Chem. Phys. 1994, 101, 5957.
53. For a review on the CASSCF scheme, see: Roos. B. O. In Lecture Notes in Quantum Chemistry; Roos, B. O., Ed.; Springer: Berlin, 1992.
54. McDouall, J. J. W.; Peasley, K.; Robb, M. A. Chem. Phys. Lett. 1988, 148, 183.
55. Parr, R. G.; Yang, W. Density Functional Theory of Atoms and Molecules; Oxford University Press: Oxford 1989.
56. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 1372.
57. (b) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
58. Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
59. Pople, J. A.; Scott, A. P.; Wong, M. W.; Radom, L. Isr. J. Chem. 1993, 33, 345.
60. van Garderen, H. F.: Ruttink, P. J. A.; Burgers, P. C.; McGibbon, G. A.; Terlouw, J. K. Int. J. Mass Spectrom. Ion Processes 1992, 121, 159.
61. Busch, K. L.; Glish, G. L.; McLuckey, S. A. Mass Spectrometry/ Mass Spectrometry, Techniques and Applications of Tandem Mass Spectrometry: VCH: New York, 1988.
62. Beynon, J. H.; Hopkinson, J. A.; Lester, G. R. Int. J. Mass Spectrom. Ion Physics 1969, 2, 291.
63. (a) Burgers, P. C.; Holmes, J. L.; Terlouw, J. K. J. Am. Chem. Soc. 1984, 106, 2762.
64. (b) Burgers, P. C.; Terlouw, J. K.; Weiske, T.; Schwarz, H. Chem. Phys. Lett. 1986, 132, 69.
65. (a) Burgers, P. C.; McGibbon, G. A.; Terlouw, J. K. Chem. Phys. Lett. 1994, 224, 539.
66. (b) Wiedmann, F. A.; Cai, J.; Wesdemiotis, C. Rapid Commun. Mass Spectrom. 1994, 8, 804.
67. Schröder, D.; Müller, J.; Schwarz, H. Organometallics 1993, 12, 1972.
68. BDE (C-H) = 134 kcal/mol according to data: Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D. J. Phys. Chem. Ref. Data 1988, 17, Suppl. 1.
69. Emmanuel, C. J.; Shelvin, P. B. J. Am. Chem. Soc. 1994, 116, 5991.
70. (a) Tantardini, G. F.; Simonetta, M. Int. J. Quant. Chem. 1981, 20, 705.
71. (b) Walker, I. C.; Palmer, M. H.; Hopkirk, A. Chem. Phys. 1990, 141, 365.
72. (c) Nakano, H.; Nakajima, T.; Obara, S. Chem. Phys. Lett. 1991, 177, 458.
73. (d) Foresman, J. B.; Head-Gordon, M.; Pople, J. A.; Frisch, M. J. J. Phys. Chem. 1992, 96, 135.
74. (e) Fulscher, M. P.; Andersson, K.; Roos, B. O. J. Phys. Chem. 1992, 96, 9204.
75. See, e.g.; Liebman, J. F.; Simons, J. In Molecular Structure and Energetics, Liebman, J. F., Greenberg, A., Eds., VCH: Deerfield Beach, FL, 1986; Vol. I.
76. Due to the loss of symmetry in the saddle points and the importance of the C-H and N-H bonds being formed or broken in the rearrangement processes, no straightforward selection of an active space, which is consistent with the description of the minima and at the time still manageable computationally, was possible. We therefore limited our CASSCF/MP2 calculations to the minima.
77. Baker, J.; Scheiner, A.; Andzelm, A. Chem. Phys. Lett. 1993, 216, 380.
78. Spitzner, D. In Houhen-Weyl; Band E7b, Teil 2, Georg Thieme Verlag: Stuttgart, Germany, 1992; p 286.
79. Lifshitz, C. J. Phys. Chem. 1982, 86, 606.
80. Burgers, P. C.; Holmes, J. L. Org. Mass Spectrom. 1982, 17, 123.
81. Lias, S. G.; Liebman, J. F.; Levin, R. D. J. Phys. Chem. Ref. Data 1984, 13, 695.
82. A purely calculated PA needs to be corrected for ZPE and thermodynamic contributions (entropy). Dixon, D. A.; Lias, S. G. In Molecular Structure and Energetics; Liebman, J. F., Greenberg, A., Eds.; VCH Publishers: Deerfield Beach, FL, 1987; Vol. 2, Chapter 7, p 269.