The Bond Localization Energies in the Aromatic Bismethano[14]annulenes†
Maja Nendel
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569 (USA), Fax: Int. code +(310) 206-1843, e-mail: [email protected]
Search for more papers by this authorCorresponding Author
Prof. Dr. Kendall N. Houk
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569 (USA), Fax: Int. code +(310) 206-1843, e-mail: [email protected]
Kendall N. Houk, Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569 (USA), Fax: Int. code +(310) 206-1843, e-mail: [email protected]
Paul von Ragué Schleyer, Computer-Chemie-Centrum, Institut für Organische Chemie der Universität Erlangen-Nürnberg, Henkestrasse 42, D-91054 Erlangen (Germany), Fax: Int. code +(9131) 85-9132
Search for more papers by this authorProf. Dr. L. M. Tolbert
School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332-0400 (USA)
Search for more papers by this authorProf. Dr. Emanuel Vogel
Institut für Organische Chemie der Universität Köln (Germany)
Search for more papers by this authorDr. Haijun Jiao
Computer-Chemie-Centrum, Institut für Organische Chemie der Universität Erlangen-Nürnberg, Henkestrasse 42, D-91054 Erlangen (Germany), Fax: Int. code +(9131) 85-9132
Search for more papers by this authorCorresponding Author
Prof. Dr. Paul von Ragué Schleyer
Computer-Chemie-Centrum, Institut für Organische Chemie der Universität Erlangen-Nürnberg, Henkestrasse 42, D-91054 Erlangen (Germany), Fax: Int. code +(9131) 85-9132
Kendall N. Houk, Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569 (USA), Fax: Int. code +(310) 206-1843, e-mail: [email protected]
Paul von Ragué Schleyer, Computer-Chemie-Centrum, Institut für Organische Chemie der Universität Erlangen-Nürnberg, Henkestrasse 42, D-91054 Erlangen (Germany), Fax: Int. code +(9131) 85-9132
Search for more papers by this authorMaja Nendel
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569 (USA), Fax: Int. code +(310) 206-1843, e-mail: [email protected]
Search for more papers by this authorCorresponding Author
Prof. Dr. Kendall N. Houk
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569 (USA), Fax: Int. code +(310) 206-1843, e-mail: [email protected]
Kendall N. Houk, Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569 (USA), Fax: Int. code +(310) 206-1843, e-mail: [email protected]
Paul von Ragué Schleyer, Computer-Chemie-Centrum, Institut für Organische Chemie der Universität Erlangen-Nürnberg, Henkestrasse 42, D-91054 Erlangen (Germany), Fax: Int. code +(9131) 85-9132
Search for more papers by this authorProf. Dr. L. M. Tolbert
School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332-0400 (USA)
Search for more papers by this authorProf. Dr. Emanuel Vogel
Institut für Organische Chemie der Universität Köln (Germany)
Search for more papers by this authorDr. Haijun Jiao
Computer-Chemie-Centrum, Institut für Organische Chemie der Universität Erlangen-Nürnberg, Henkestrasse 42, D-91054 Erlangen (Germany), Fax: Int. code +(9131) 85-9132
Search for more papers by this authorCorresponding Author
Prof. Dr. Paul von Ragué Schleyer
Computer-Chemie-Centrum, Institut für Organische Chemie der Universität Erlangen-Nürnberg, Henkestrasse 42, D-91054 Erlangen (Germany), Fax: Int. code +(9131) 85-9132
Kendall N. Houk, Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569 (USA), Fax: Int. code +(310) 206-1843, e-mail: [email protected]
Paul von Ragué Schleyer, Computer-Chemie-Centrum, Institut für Organische Chemie der Universität Erlangen-Nürnberg, Henkestrasse 42, D-91054 Erlangen (Germany), Fax: Int. code +(9131) 85-9132
Search for more papers by this authorThis work was supported by the U.S. National Science Foundation and the San Diego Supercomputer Center at UCLA, and by the Fonds der Chemischen Industrie, the Deutsche Forschungsgemeinschaft, the Stiftung Volkswagenwerk, and the Convex Computer Corporation in Erlangen. Support from the Alexander-von-Humboldt Foundation made this collaboration possible.
Graphical Abstract
An energy increase of only 6 kcal mol−1 is associated with the double-bond localization of the aromatic syn-bismethano[14]annulene (1). The correct prediction of aromaticity is surprisingly difficult, as shown by comparison of several theoretical predictions to experimental results.
References
- 1(a)
P. von R. Schleyer,
H. Jiao,
Pure Appl. Chem.
1996,
68, 209;
10.1351/pac199668020209 Google Scholar(b) P. von R. Schleyer, P. Freeman, H. Jiao, B. Goldfuss, Angew. Chem. 1995, 107, 332;10.1002/ange.19951070309 Google ScholarAngew. Chem. Int. Ed. Engl. 1995, 34, 337; (c) P. von R. Schleyer, C. Maerker, A. Dransfeld, H. Jiao, N. J. R. van, E. Hommes, J. Am. Chem. Soc. 1996, 118, 6317; (d) V. I. Minkin, M. N. Glukhovtsev, B. Y. Simkin, Aromaticity and Antiaromaticity, Wiley, New York, 1994.
- 2(a)
H.-B. Bürgi,
K. K. Baldridge,
K. Hardcastle,
N. L. Frank,
P. Gantzel,
J. S. Siegel,
J. Ziller,
Angew. Chem.
1995,
107, 1575;
Angew. Chem Int. Ed. Engl.
1995,
34, 1454;
(b)
F. Cardullo,
D. Giuffrida,
F. H. Kohnke,
F. M. Raymo,
J. F. Stoddart,
D. J. Williams,
Angew. Chem Int. Ed. Engl.
1996,
108, 347 and
10.1002/ange.19961080319 Google ScholarAngew. Chem Int. Ed. Engl. 1996, 35, 339.
- 3(a) P. C. Hiberty, D. Danovich, A. Shurki, S. Shaik, J. Am. Chem. Soc. 1995, 117, 7760, and references therein; (b) E. D. Glendening, R. Faust, A. Streitwieser, K. P. C. Vollhardt, F. Weinhold, J. Am. Chem. Soc. 1993, 115, 10952; (c) R. Faust, E. D. Glendening, A. Streitwieser, K. P. C. Vollhardt, J. Am. Chem. Soc. 1992, 114, 8263; (d) S. Shaik, A. Shurki, D. Danovich, P. C. Hiberty, J. Am. Chem. Soc. 1996 118, 666; (e) Y. Haas, S. Zilberg, J. Am. Chem. Soc. 1995, 117, 5387; (f) S. Shaik, S. Zilberg, Y. Haas, Acc. Chem. Res. 1996, 29, 211; (g) L. A. Curtiss, K. Raghavachari, P. C. Redfern, J. A. Pople, Chem. Phys. 1997, 106, 1036.
- 4 R. H. Mitchell, Y. S. Chen, V. S. Iyer, D. Y. K. Lau, K. K. Baldridge, J. S. Siegel, J. Am. Chem. Soc. 1996, 118, 2907.
- 5 H. M. Sulzbach, P. von R. Schleyer, H. Jiao, Y. Xie, H. F. Schaefer, III, J. Am. Chem. Soc. 1995, 117, 1369.
- 6 D. A. Plattner, K. N. Houk, J. Am. Chem. Soc. 1995, 117, 1369.
- 7 H. M. Sulzbach, H. F. Schaefer, III, W. Klopper, H. P. Lüthi, J. Am. Chem. Soc. 1996, 118, 3519.
- 8 E. Vogel, J. Sombroek, W. Wagemann, Angew. Chem. 1975, 87, 591; Angew. Chem. Int. Ed. Engl. 1975, 14, 564.
- 9
E. Vogel,
U. Haberland,
H. Günther,
Angew. Chem.
1970,
82, 510;
10.1002/ange.19700821304 Google ScholarAngew. Chem. Int. Ed. Engl. 1970, 9, 513.
- 10 R. Destro, T. Pilati, M. Simonetta, Acta Crystallogr. Sect. B 1977, 33, 940.
- 11 C. M. Gramacioli, A. S. Mimun, A. Mugnoli, M. Simonetta, J. Am. Chem. Soc. 1973, 95, 3149.
- 12 The calculations were performed with the GAUSSIAN94 program: Gaussian 94, Revision C. 2, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1995.
- 13 Although correlation energy is, in principle, included in the PM3 parametrization, the method is more suited for localized bond systems than for delocalized.
- 14 R. L. Disch, J. M. Schulman, Chem. Phys. Lett. 1988, 152, 402–404.
- 15
K. N. Houk,
Y. Li,
J. D. Evanseck,
Angew. Chem.
1991,
104, 711;
10.1002/ange.19921040606 Google ScholarAngew. Chem. Int. Ed. Engl. 1991, 31, 682.
- 16 J. A. Pople, R. D. Adamson, P. M. W. Gill, J. Phys. Chem. 1996, 100, 6348, and references therein.
- 17
Magnetic susceptibilities have been calculated using Kutzelnigg's IGLO method (Individual Gauge for Localized Orbitals) with the DZ basis set (constructed from Huzinaga 7s3p set for carbon (4111/21) and 3s set for hydrogen (21): (a) W. Kutzelnigg).
Isr. J. Chem.
1980,
19, 193;
(b)
M. Schindler,
W. Kutzelnigg.
J. Chem. Phys.
1982,
76, 1910;
(c)
W. Kutzelnigg,
U. Fleisher,
M. Schindler,
NMR Basic Princ. Prog.
1990,
23, 165.
10.1007/978-3-642-75932-1_3 Google Scholar
- 18 A. Julg, P. François, Theoret. Chim. Acta 1967, 8, 249. A = 1 – (225/ n) Σ[1–(ri/ r)]2 where n is the number of CC bonds, ri is an individual CC bond length.
- 19 U. Fleischer, W. Kutzelnigg, P. Lazzeretti, V. Mühlenkamp, J. Am. Chem. Soc. 1994, 116, 5298; (b) H. Jiao, P. von R. Schleyer, K. K. Baldridge, J. S. Siegel, Angew. Chem. submitted.
- 20(a) P. R. Taylor, E. Bylaska, J. H. Weare, R. Kawai, Chem. Phys. Lett. 1995, 235, 558; (b) J. M. L. Martin, P. R. Talyor, Chem. Phys. Lett. 1995, 240, 521; (c) G. E. Scuseria, Science 1996, 271, 942; (d) D. Bakowies, M. Bühl, W. Thiel. Am. Chem. Soc. 1995, 117, 10113.
- 21 D. Bakowies, W. Thiel, J. Am. Chem. Soc. 1991, 113, 3704.
- 22(a) W. L. Jorgensen, J. Am. Chem. Soc. 1975, 97, 3082–3090; (b) W. T. Borden, S. D. Young, D. C. Frost, N. P. Westwood, W. L. Jorgensen, J. Org. Chem. 1979, 44, 737, and references therein.
