α-Stabilization of carbanions: Fluorine is more effective than the heavier halogens

Angewandte Chemie - International Edition

Volumn 45, Issue 5, 2006, Pages 823-826

  Bickelhaupt, F Matthias ^a   Hermann, Holger L ^b   Boche, Gernot ^b  

^a VU UNIVERSITY AMSTERDAM   (Netherlands)

^b PHILIPPS UNIVERSITY MARBURG   (Germany)

Author keywords

stabilization; Bond theory; Carbanions; Density functional calculations; Substituent effects

Indexed keywords

ALKALINITY; CARBON; FLUORINE; HALOGEN COMPOUNDS; PROBABILITY DENSITY FUNCTION;

Α-STABILIZATION; BOND THEORY; CARBANIONS; DENSITY FUNCTIONAL CALCULATIONS; SUBSTITUENT EFFECTS;

NEGATIVE IONS;

EID: 31444445628     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200501633     Document Type: Article

References (47)

1. a) F. A. Carey, R. J. Sundberg, Advanced Organic Chemistry, Part A, 4th ed., Kluwer Academic/Plenum, New York, 2001;
2. b) J. March, Advanced Organic Chemistry, 4th ed., Wiley-Interscience, New York, 1992;
3. c) Lithium Chemistry: A Theoretical and Experimental Overview (Eds.: A.-M. Sapse, P. von R. Schleyer), Wiley, New York, 1995.
4. See also, for example: a) M. Shimizu, T. Hiyama, Angew. Chem. 2005, 117, 218;
5. Angew. Chem. Int. Ed. 2005, 44, 214;
6. b) D. M. Hodgson, Y. K. Chung, J. M. Paris, J. Am. Chem. Soc. 2004, 126, 8664;
7. c) P. Knochel, W. Dohle, N. Gommermann, F. F. Kneisel, F. Kopp, T. Korn, I. Sapountzis, V. A. Vu, Angew. Chem. 2003, 115, 4438;
8. Angew. Chem. Int. Ed. 2003, 42, 4302;
9. d) M. Schlosser, Angew. Chem. 1998, 110, 1538;
10. Angew. Chem. Int. Ed. 1998, 37, 1496;
11. e) D. Seebach, Angew. Chem. 1990, 102, 1363;
12. Angew. Chem. Int. Ed. Engl. 1990, 29, 1320;
13. f) G. Boche, Angew. Chem. 1989, 101, 286;
14. Angew. Chem. Int. Ed. Engl. 1989, 28, 271;
15. g) D. Seebach, H. Siegel, J. Gabriel, R. Hässig, Helv. Chim. Acta 1980, 63, 2046;
16. h) D. Seebach, H. Siegel, K. Müllen, K. Hiltbrunner, Angew. Chem. 1979, 91, 844;
17. Angew. Chem. Int. Ed. Engl. 1979, 18, 784;
18. i) H. Siegel, K. Hiltbrunner, D. Seebach, Angew. Chem. 1979, 91, 845;
19. Angew. Chem. Int. Ed. Engl. 1979, 18, 785.
20. +) for both, structure and reactivity, of these species,
21. b) Details of the calculations: H. Hermann, J. C. W. Lohrenz, A. Kühn, G. Boche, Tetrahedron 2000, 56, 4109.
22. See, for example: a) B. Römer, G. G. Gatev, M. Zhong, J. I. Brauman, J. Am. Chem. Soc. 1998, 120, 2919;
23. b) S. Ingemann, N. M. M. Nibbering, J. Chem. Soc. Perkin Trans. 2 1985, 837;
24. c) S. Ingemann, N. M. M. Nibbering, Can. J. Chem. 1984, 62, 2273;
25. d) J. E. Bartmess, R. L. Hays, H. N. Khatri, R. N. Misra, S. R. Wilson, J. Am. Chem. Soc. 1981, 103, 4747;
26. e) NIST Computational Chemistry Comparison and Benchmark Database, NIST Standard Reference Database Number 101, Release 11, May 2005 (Ed.: R. D. Johnson III), http://srdata.nist.gov/cccbdb.
27. See, for example: a) P. M. Mayer, L. Radom, J. Phys. Chem. A 1998, 102, 4918;
28. b) H. J. Castejon, K. B. Wiberg, J. Org. Chem. 1998, 63, 3937;
29. c) K. B. Wiberg, H. Castejon, J. Am. Chem. Soc. 1994, 116, 10489;
30. d) A. M. El-Nahas, P. v. R. Schleyer, J. Comput. Chem. 1994, 15, 596;
31. e) C. F. Rodriquez, S. Sirois, A. C. Hopkinson, J. Org. Chem. 1992, 57, 4869;
32. f) F. Bernardi, A. Bottoni, A. Venturini, A. Mangini, J. Am. Chem. Soc. 1986, 108, 8171;
33. g) P. v. R. Schleyer, T. Clark, A. J. Kos, G. W. Spitznagel, C. Rohde, D. Arad, K. N. Houk, N. G. Rondan, J. Am. Chem. Soc. 1984, 106, 6467;
34. h) J. R. Larson, N. D. Epiotis, J. Am. Chem. Soc. 1981, 103, 410.
35. a) G. te Velde, F. M. Bickelhaupt, S. J. A. van Gisbergen, C. Fonseca Guerra, E. J. Baerends, J. G. Snijders, T. Ziegler, J. Comput. Chem. 2001, 22, 931;
36. b) C. Fonseca Guerra, J. G. Snijders, G. te Velde, E. J. Baerends, Theor. Chem. Acc. 1998, 99, 391;
37. c) The TZ2P basis set consists of Slater-type orbitals (STOs) and is of triple-ζ quality, augmented with two sets of polarization functions on H (2p and 3d), C, N, O, F, Si, P, S, Cl, Br, and I (3d and 4f).
38. F. M. Bickelhaupt, E. J. Baerends in Rev. Comput. Chem, Vol. 15 (Eds.: K. B. Lipkowitz, D. B. Boyd), Wiley-VCH, New York, 2000, pp. 1-86.
39. a) Basis sets for ab initio MP2(full)//MP2(full) computations: 6-311 + + G(d,p) for H, C, N, O, F, Si, P, S, Cl, and (4111/3111/1) with relativistic effective core potential for Br, I, see: A. Bergner, M. Dolg, W. Küchle, H. Stoll, H. Preuß, Mol. Phys. 1993, 80, 1431;
40. b) ab initio computations were carried out with Gaussian 98 (Revision A.7), M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. C. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998.
41. In fact, this is exactly what one would expect based on qualitative molecular orbital theory. For an excellent introduction into and overview of molecular orbital theory, see, for example: a) R. Hoffmann, Angew. Chem. 1982, 94, 725;
42. Angew. Chem. Int. Ed. Engl. 1982, 21, 711;
43. b) T. A. Albright, J. K. Burdett, M.-H. Whangbo, Orbital Interactions in Chemistry, Wiley-Interscience, New York, 1985.
44. This agrees nicely with the following studies: a) A. Shurki, P. C. Hiberty, S. Shaik, J. Am. Chem. Soc. 1999, 121, 822;
45. b) L. Deng, V. Branchadell, T. Ziegler, J. Am. Chem. Soc. 1994, 116, 10645;
46. See also c) F. M. Bickelhaupt, T. Ziegler, P. v. R. Schleyer, Organometallics 1996, 15, 1477.
47. 3-X.