Bishomoaromatic 1,2,4-triboracyclopentane dianions: Strong three-center, two-electron bonds between three boron atoms

Angewandte Chemie - International Edition

Volumn 39, Issue 7, 2000, Pages 1272-1275

  Scheschkewitz, David ^a   Ghaffari, Abolfazl ^a   Amseis, Peter ^a   Unverzagt, Markus ^a   Subramanian, Govindan ^b   Hofmann, Matthias ^b   Von Schleyer, Paul Ragué ^b   Schaefer III, Henry F ^b   Geiseler, Gertraud ^a   Massa, Werner ^a   Berndt, Armin ^a  

^a PHILIPPS UNIVERSITY MARBURG   (Germany)

^b UNIVERSITY OF GEORGIA   (United States)

Author keywords

Ab initio calculations; Anions; Boron

Indexed keywords

BISHOMOAROMATIC 1,2,4 TRIBORACYCLOPENTANE DIANION; BORON; CYCLOPENTANE DERIVATIVE; UNCLASSIFIED DRUG;

ANALYTIC METHOD; ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CRYSTAL STRUCTURE; DATA ANALYSIS; DRUG SYNTHESIS; ELECTRON TRANSPORT; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 0034599663     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(20000403)39:7<1272::AID-ANIE1272>3.0.CO;2-Z     Document Type: Article

References (33)

1. S. Winstein, M. Shatavsky, C. Norton, R. B. Woodward, J. Am. Chem. Soc. 1955, 77, 4183;
2. W. G. Woods, R. A. Carboni, J. D. Roberts, J. Am. Chem. Soc. 1956, 78, 5653.
3. a) M. Bremer, K. Schötz, P. von R. Schleyer, U. Fleischer, M. Schindler, W. Kutzelnigg, W. Koch, P. Pulay, Angew. Chem. 1989, 101, 1063,
4. Angew. Chem. Int. Ed. Engl. 1989, 25, 1042;
5. b) P. von R. Schleyer, C. Maerker, Pure Appl. Chem. 1995, 67, 755.
6. a) T. Laube, J. Am. Chem. Soc. 1989, 111, 9224;
7. b) T. Laube, C. Lohse, J. Am. Chem. Soc. 1994, 116, 9001, and references therein;
8. T. Laube, Acc. Chem. Res. 1995, 28, 399;
9. W. J. Evans, K. J. Forrestal, J. W. Ziller, J. Am. Chem. Soc. 1995, 117, 12635.
10. G. A. Olah, G. Liang, J. Am. Chem. Soc. 1975, 97, 6803;
11. G. A. Olah, A. L. Berrier, M. Arvanaghi, G. K. Surya Prakash, J. Am. Chem. Soc. 1981, 103, 1122.
12. P. von R. Schleyer, T. W. Bentley, W. Koch, A. J. Kos, H. Schwarz, J. Am. Chem. Soc. 1987, 109, 6953;
13. K. J. Szabo, E. Kraka, D. Cremer, J. Org. Chem. 1996, 67, 2783.
14. [7] describes a trishomoaromatic 1,3,5-triboracyclohexane dianion, a system isoelectronic with the trishomocyclopropenylium cation.
15. W. Lößlein, H. Pritzkow, P. von R. Schleyer, L. Schmitz, W. Siebert, Angew. Chem. 2000, 112, 1336,
16. Angew. Chem. Int. Ed. 2000, 39, 1297.
17. T. Totani, K. Tori, J. Murakami, H. Watanabe, Org. Magn. Reson. 1971, 3, 627.
18. The geometries of the dianions were optimized at the MP2(fc)/6-31+G* level, while MP2(fc)/6-31G* was applied for the cations. Relative energies were corrected for scaled (0.89) zero-point vibrational energies from HF/6-31G* frequency calculations. Chemical shifts were computed at the GIAO-SCF/6-311+G** level employing the optimized geometries. The Gaussian 94 program was used for all computations: 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 94 Revision C.3, Gaussian, Inc., Pittsburgh PA, 1995.
19. A. Höfner, B. Ziegler, W. Massa, A. Beredt, Angew. Chem. 1989, 101, 188;
20. Angew. Chem. Int. Ed. Engl. 1989, 28, 186.
21. M. Unverzagt, G. Subramanian, M. Hofmann, P. von R. Schleyer, S. Berger, K. Harms, W. Massa, A. Berndt, Angew. Chem. 1997, 109, 1567;
22. Angew. Chem. Int. Ed. Engl. 1997, 36, 1469.
23. 2O). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
24. Similar lithium cation coordinations were found recently for 1,2-diboratacyclopentadienides: D. Scheschkewitz, M. Hofmann, P. von R. Schleyer, G. Geiseler, W. Massa, A. Berndt, Angew. Chem. 1999, 111, 3116;
25. Angew. Chem. Int. Ed. 1999, 38, 2936.
26. Quantum Chemistry Archive, Computer Chemie Centrum, Universität Erlangen-Nürnberg.
27. -1 (MP2(fc)/6-31G* + 0.89 ZPE(HF/6-31G*)) relative to the corresponding classical structures 4u-R.
28. 11B = -2 is observed experimentally for 5b.
29. B. Wrackmeyer, Z. Naturforsch. B 1980, 35, 439, and references therein.
30. M. Hofmann, D. Scheschkewitz, A. Ghaffari, G. Geiseler, W. Massa, H. F. Schaefer, A. Berndt, J. Mol. Model. 2000, 6, in press.
31. R. C. Haddon, J. Org. Chem. 1979, 44, 3608;
32. R. C. Haddon, Acc. Chem. Res. 1988, 21, 243.
33. V. I. Minkin, M. N. Glukhovtsev, B. Y. Simkin, Aromaticity and Antiaromaticity, Wiley, New York, 1994, p. 243.