Structural consequences of π-donation by NR2 groups: Ab initio study of tetrakis(dimethylamino)ethylene (TDAE) and its unsubstituted analog

Journal of Physical Chemistry A

Volumn 102, Issue 49, 1998, Pages 10151-10158

  Fleurat Lessard, Paul ^a   Volatron, François ^a  

^a UNIVERSITÉ PARIS SACLAY   (France)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001005320     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp982802a     Document Type: Article

References (22)

1. Bock, H.; Ruppert, K.; Näther, C.; Havlas, Z. Angew. Chem., Int. Ed. Engl. 1991, 30, 1180.
2. Gund, P. J. Chem. Educ. 1972, 49, 100.
3. Chance, J. M.; Kahr, B.; Buda, A. B.; Toscano, J. P.; Mislow, K. J. Org. Chem. 1988, 53, 3226.
4. Bock, H.; Borrmann, H.; Havlas, Z.; Oberhammer, H.; Ruppert, K.; Simon, A. Angew. Chem., Int. Ed. Engl. 1991, 30, 1678.
5. Bruckmann, J.; Krüger, C.; Borrmann, H.; Simon, A.; Bock, H. Zeitschrift für Kristallographie 1995, 210, 521.
6. Frenking, G. J. Am. Chem. Soc. 1991, 113, 2476.
7. Hehre, W. J.; Ditchfield, R.; Pople, J. J. Chem. Phys. 1972, 56, 2257. Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213.
8. Hehre, W. J.; Ditchfield, R.; Pople, J. J. Chem. Phys. 1972, 56, 2257. Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213.
9. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; 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 94, Revision E.1; Gaussian, Inc.: Pittsburgh, PA, 1995.
10. In this study, we have restricted ourselves to geometries with six π-electrons (two from the C=C double bond and four from the two nitrogen lone pairs), except for the fully conjugated or deconjugated geometries (3 and 4, respectively). Test calculations on structures with one or three deconjugated lone pairs have shown they lie higher in energy.
11. Klein, J. Tetrahedron 1983, 39, 2733. Klein, J.; Medlik, A. J. Chem. Soc,. Chem. Commun. 1973, 275. Agranat, I.; Skancke, A. J. Am. Chem. Soc. 1985, 107, 867. Wiberg, K. B. J. Am. Chem. Soc. 1990, 112, 4177. Agranat, I.; Radhakrishnan, T. P.; Herndon, W. C.; Skancke, A. Chem. Phys. Lett. 1991, 181, 117. Gobbi, A.; MacDougall, P. J.; Frenking, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 1001. Frenking, G.; Gobbi, A. Chem. Phys. Lett. 1992, 197, 335. Skancke, A. J. Phys. Chem. 1994, 98, 5234.
12. Klein, J. Tetrahedron 1983, 39, 2733. Klein, J.; Medlik, A. J. Chem. Soc,. Chem. Commun. 1973, 275. Agranat, I.; Skancke, A. J. Am. Chem. Soc. 1985, 107, 867. Wiberg, K. B. J. Am. Chem. Soc. 1990, 112, 4177. Agranat, I.; Radhakrishnan, T. P.; Herndon, W. C.; Skancke, A. Chem. Phys. Lett. 1991, 181, 117. Gobbi, A.; MacDougall, P. J.; Frenking, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 1001. Frenking, G.; Gobbi, A. Chem. Phys. Lett. 1992, 197, 335. Skancke, A. J. Phys. Chem. 1994, 98, 5234.
13. Klein, J. Tetrahedron 1983, 39, 2733. Klein, J.; Medlik, A. J. Chem. Soc,. Chem. Commun. 1973, 275. Agranat, I.; Skancke, A. J. Am. Chem. Soc. 1985, 107, 867. Wiberg, K. B. J. Am. Chem. Soc. 1990, 112, 4177. Agranat, I.; Radhakrishnan, T. P.; Herndon, W. C.; Skancke, A. Chem. Phys. Lett. 1991, 181, 117. Gobbi, A.; MacDougall, P. J.; Frenking, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 1001. Frenking, G.; Gobbi, A. Chem. Phys. Lett. 1992, 197, 335. Skancke, A. J. Phys. Chem. 1994, 98, 5234.
14. Klein, J. Tetrahedron 1983, 39, 2733. Klein, J.; Medlik, A. J. Chem. Soc,. Chem. Commun. 1973, 275. Agranat, I.; Skancke, A. J. Am. Chem. Soc. 1985, 107, 867. Wiberg, K. B. J. Am. Chem. Soc. 1990, 112, 4177. Agranat, I.; Radhakrishnan, T. P.; Herndon, W. C.; Skancke, A. Chem. Phys. Lett. 1991, 181, 117. Gobbi, A.; MacDougall, P. J.; Frenking, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 1001. Frenking, G.; Gobbi, A. Chem. Phys. Lett. 1992, 197, 335. Skancke, A. J. Phys. Chem. 1994, 98, 5234.
15. Klein, J. Tetrahedron 1983, 39, 2733. Klein, J.; Medlik, A. J. Chem. Soc,. Chem. Commun. 1973, 275. Agranat, I.; Skancke, A. J. Am. Chem. Soc. 1985, 107, 867. Wiberg, K. B. J. Am. Chem. Soc. 1990, 112, 4177. Agranat, I.; Radhakrishnan, T. P.; Herndon, W. C.; Skancke, A. Chem. Phys. Lett. 1991, 181, 117. Gobbi, A.; MacDougall, P. J.; Frenking, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 1001. Frenking, G.; Gobbi, A. Chem. Phys. Lett. 1992, 197, 335. Skancke, A. J. Phys. Chem. 1994, 98, 5234.
16. Klein, J. Tetrahedron 1983, 39, 2733. Klein, J.; Medlik, A. J. Chem. Soc,. Chem. Commun. 1973, 275. Agranat, I.; Skancke, A. J. Am. Chem. Soc. 1985, 107, 867. Wiberg, K. B. J. Am. Chem. Soc. 1990, 112, 4177. Agranat, I.; Radhakrishnan, T. P.; Herndon, W. C.; Skancke, A. Chem. Phys. Lett. 1991, 181, 117. Gobbi, A.; MacDougall, P. J.; Frenking, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 1001. Frenking, G.; Gobbi, A. Chem. Phys. Lett. 1992, 197, 335. Skancke, A. J. Phys. Chem. 1994, 98, 5234.
17. Klein, J. Tetrahedron 1983, 39, 2733. Klein, J.; Medlik, A. J. Chem. Soc,. Chem. Commun. 1973, 275. Agranat, I.; Skancke, A. J. Am. Chem. Soc. 1985, 107, 867. Wiberg, K. B. J. Am. Chem. Soc. 1990, 112, 4177. Agranat, I.; Radhakrishnan, T. P.; Herndon, W. C.; Skancke, A. Chem. Phys. Lett. 1991, 181, 117. Gobbi, A.; MacDougall, P. J.; Frenking, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 1001. Frenking, G.; Gobbi, A. Chem. Phys. Lett. 1992, 197, 335. Skancke, A. J. Phys. Chem. 1994, 98, 5234.
18. Klein, J. Tetrahedron 1983, 39, 2733. Klein, J.; Medlik, A. J. Chem. Soc,. Chem. Commun. 1973, 275. Agranat, I.; Skancke, A. J. Am. Chem. Soc. 1985, 107, 867. Wiberg, K. B. J. Am. Chem. Soc. 1990, 112, 4177. Agranat, I.; Radhakrishnan, T. P.; Herndon, W. C.; Skancke, A. Chem. Phys. Lett. 1991, 181, 117. Gobbi, A.; MacDougall, P. J.; Frenking, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 1001. Frenking, G.; Gobbi, A. Chem. Phys. Lett. 1992, 197, 335. Skancke, A. J. Phys. Chem. 1994, 98, 5234.
19. Volatron, F.; Demachy, I. Chem. Phys. Lett. 1992, 198, 253.
20. Lehn, J. M. Fort. Chem. Forsch. 1970, 15, 311.
21. The absolute energy of 8′ is -610.340 29 au at the HF level. The stabilization of 8′ with respect to 4′ is equal to -23.3 kcal/mol.
22. The absolute energy of 8′ is -612.314 08 au at the MP2/HF level.