Facile formation of a persistent butadien-2-yl cation stabilized by hyperconjugation with an Al-C bond

Angewandte Chemie - International Edition

Volumn 45, Issue 26, 2006, Pages 4358-4361

  Uhl, Werner ^a   Grunenberg, Jörg ^b   Hepp, Alexander ^a   Matar, Madhat ^a   Vinogradov, Andrej ^a  

^a UNIVERSITY OF MÜNSTER   (Germany)

^b TECHNICAL UNIVERSITY OF BRAUNSCHWEIG   (Germany)

Author keywords

Aluminum; Hydroalumination; Hyperconjugation; Structure elucidation; Vinyl cation

Indexed keywords

ALUMINUM; CHELATION; CHEMICAL BONDS; COMPLEXATION; COORDINATION REACTIONS; REACTION KINETICS; SYNTHESIS (CHEMICAL);

HYDROALUMINATION; HYPERCONJUGATION; STRUCTURE ELUCIDATION; VINYL CATION;

ORGANOMETALLICS;

EID: 33746292209     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200504428     Document Type: Article

References (29)

1. C. Elschenbroich, Organometallchemie, 4th ed., Teubner, Stuttgart, 2003;
2. Hollemann-Wiberg, Lehrbuch der Anorganischen Chemie, deGruyter, Berlin, 1995.
3. W. Uhl, F. Breher, Angew. Chem. 1999, 111, 1578;
4. Angew. Chem. Int. Ed. 1999, 38, 1477;
5. W. Uhl, F. Breher, A. Lützen, W. Saak, Angew. Chem. 2000, 112, 414;
6. Angew. Chem. Int. Ed. 2000, 39, 406;
7. W. Uhl, Inorganic Chemistry Highlights (Eds.: G. Meyer, D. Naumann, L. Wesemann), Wiley-VCH, Weinheim, 2002, p. 229.
8. W. Uhl, F. Breher, S. Haddadpour, Organometallics 2005, 24, 2210;
9. W. Uhl, S. Haddadpour, M. Matar, Organometallics 2006, 25, 159.
10. W. Uhl, F. Breher, J. Organomet. Chem. 2000, 608, 54.
11. -3. The tert-butyl groups of CT1 and CT2 are rotationally disordered. The methyl groups were refined in three positions with occupancy factors of 0.3333 (each position at CT1) and 0.5000, 0.2500, and 0.2500 (CT2) with restrictions of bond lengths and angles. CCDC-292841 (3) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
12. J. March, Advanced Organic Chemistry, 3rd ed., Wiley, New York, 1985, p. 19.
13. Geometry optimizations, calculation of frequencies, and NMR parameters (B3LYP 6-31G(d) GIAO) were conducted with the Gaussian program package: Gaussian03, Revision C.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Wallingford CT, 2004.
14. The generalized compliance constants were calculated with the program Compliance (K. Brandhorst, J. Grunenberg, Braunschweig, 2005) and are based on the B3LYP/6-13G(d) Cartesian force constants.
15. For details of this method, see: G. v. Frantzius, R. Streubel, K. Brandhorst, J. Grunenberg, Organometallics 2006, 25, 118.
16. W. Uhl, T. Spies, R. Koch, W. Saak, Organometallics 1999, 18, 4598.
17. H.-U. Siehl, H. Mayr, J. Am. Chem. Soc. 1982, 104, 909;
18. theory: H.-U. Siehl, S. Brixner, J. Phys. Org. Chem. 2004, 17, 1039;
19. Y. Apeloig, A. Stanger, J. Org. Chem. 1982, 47, 1462;
20. K. van Alem, G. Lodder, H. Zuilhof, J. Phys. Chem. A 2002, 106, 10 681;
21. K. van Alem, G. Lodder, H. Zuilhof, J. Phys. Chem. A 2000, 104, 2780;
22. A. Cunje, C. F. Rodriquez, M. H. Lien, A. C. Hopkinson, J. Org. Chem. 1996, 61, 5212.
23. T. Müller, M. Juhasz, C. A. Reed, Angew. Chem. 2004, 116, 1569;
24. Angew. Chem. Int. Ed. 2004, 43, 1546;
25. T. Müller, D. Margraf, Y. Syha, J. Am. Chem. Soc. 2005, 127, 10 852;
26. T. Müller, R. Meyer, D. Lennartz, H.-U. Siehl, Angew. Chem. 2000, 112, 3203;
27. Angew. Chem. Int. Ed. 2000, 39, 3074, and references therein.
28. L. I. Zakharkin, V. V. Kobak, J. Organomet. Chem. 1984, 270, 229.
29. W. Uhl, L. Cuypers, R. Graupner, J. Molter, A. Vester, B. Neumüller, Z. Anorg. Allg. Chem. 2001, 627, 607.