Transition regions in the Cope rearrangement of 1,5-hexadiene and its cyano derivatives

Journal of the American Chemical Society

Volumn 122, Issue 30, 2000, Pages 7377-7385

  Staroverov, Viktor N ^a   Davidson, Ernest R ^a  

^a INDIANA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; NITRILE;

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; CONFORMATION; ENERGY; GEOMETRY; MOLECULAR STABILITY; REACTION ANALYSIS;

EID: 0034596302     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja001259k     Document Type: Article

References (45)

1. Gajewski, J. J. Hydrocarbon Thermal Isomerizations; Academic: New York, 1981; pp 166-176.
2. (a) Borden, W. T.; Loncharich, R. J.; Houk, K. N. Annu. Rev. Phys. Chem. 1988, 39, 213-236.
3. (b) Dewar, M. J. S.; Jie, C. Acc. Chem. Res. 1992, 25, 537-543.
4. (c) Wiest, O.; Montiel, D. C.; Houk, K. N. J. Phys. Chem. A 1997, 101, 8378-8388.
5. (a) Doering, W. v. E.; Roth, W. R. Tetrahedron 1962, 18, 67-74.
6. (b) Hill, R. K.; Gilman, N. W. Chem. Commun. 1967, 619-620.
7. Andersson, K.; Malmqvist, P.-Å.; Roos, B. O. J. Chem. Phys. 1992, 96, 1218-1226.
8. (a) Kozlowski, P. M.; Davidson, E. R. J. Chem. Phys. 1994, 100, 3672-3682.
9. (b) Kozlowski, P. M.; Davidson, E. R. Chem. Phys. Lett. 1994, 222, 615-620.
10. Hrovat, D. A.; Morokuma, K.; Borden, W. T. J. Am. Chem. Soc. 1994, 116, 1072-1076.
11. Kozlowski, P. M.; Dupuis, M.; Davidson, E. R. J. Am. Chem. Soc. 1995, 117, 774-778.
12. Wiest, O.; Black, K. A.; Houk, K. N. J. Am. Chem. Soc. 1994, 116, 10336-10337. The interallylic distance R = 1.971 Å reported in this work for the transition state optimized at the B3LYP/6-31G* level was later refined to 1.965 Å. Our calculations with tightened convergence optimization criteria and a considerably larger integration grid give a value of 1.9661 Å.
13. Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 334-337.
14. Staroverov, V. N.; Davidson, E. R. J. Am. Chem. Soc. 2000, 122, 186-187.
15. (a) Dewar, M. J. S.; Wade, L. E., Jr. J. Am. Chem. Soc. 1973, 95, 290-291.
16. (b) Dewar, M. J. S.; Wade, L. E., Jr. J. Am. Chem. Soc. 1977, 99, 4417-4424.
17. Wehrli, R.; Schmid, H.; Bellus, D.; Hansen, H.-J. Helv. Chim. Acta 1977, 60, 1325-1356.
18. (a) Gajewski, J. J.; Conrad, N. D. J. Am. Chem. Soc. 1978, 100, 6269-6270.
19. (b) Gajewski, J. J.; Conrad, N. D. J. Am. Chem. Soc. 1979, 101, 6693-6704.
20. (c) Gajewski, J. S. Acc. Chem. Res. 1980, 13, 142-148.
21. Doering, W. v. E.; Wang, Y. J. Am. Chem. Soc. 1999, 121, 10112-10118.
22. Doering, W. v. E.; Wang, Y. J. Am. Chem. Soc. 1999, 121, 10967-10975.
23. Hrovat, D. A.; Beno, B. R.; Lange, H.; Yoo, H.-Y.; Houk, K. N.; Borden, W. T. J. Am. Chem. Soc. 1999, 121, 10529-10537.
24. Hrovat, D. A.; Chen, J.; Houk, K. N.; Borden, W. T. J. Am. Chem. Soc. 2000, in press.
25. Hrovat, D. A.; Duncan, J. A.; Borden, W. T. J. Am. Chem. Soc. 1999, 121, 169-175.
26. 2〉 in DFT.
27. Frisch, M. J.; Trucks, G. W., Schlegel, H. B., Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.6; Gaussian, Inc.: Pittsburgh, PA, 1998.
28. Dupuis, M.; Marquez, A.; Davidson, E. R. HONDO 99.6; IBM Corporation: Neighborhood Road, Kingston, NY, 1999.
29. McMurchie, L. E.; Elbert, S. T.; Langhoff, S. R.; Feller, D.; Rawlings, D. C.; Davidson, E. R. The MELD series of electronic structure codes.
30. 24
31. Dupuis, M.; Murray, C.; Davidson, E. R. J. Am. Chem. Soc. 1991, 113, 9756-9759.
32. e - 1.2 kcal/mol).
33. Doering, W. v. E.; Toscano, V. G.; Beasly, G. H. Tetrahedron 1971, 27, 5299-5306.
34. Roth, W. R.; Bauer, F.; Beitat, A.; Ebbrecht, T.; Wüstefeld, M. Chem. Ber. 1991, 124, 1453-1460.
35. 2h cut through the PES for 2-cyano-1,5-hexadiene shows that the stabilization of 2 is less than twice the stabilization of the corresponding monosubstituted structure at each value of R.
36. The density of effectively unpaired electrons is defined by the equation u(r) = 2ρ(r) - ∫p(r,r′) ρ(r′,r) dr′, where ρ(r) is the charge density and ρ(r,r′) is the reduced density matrix. As a generalization of the uncompensated spin density, the function u(r) describes the radical character of molecules of any spin multiplicity including singlets. In RHF or spin-restricted DFT for a singlet state, ρ(r,r′) is twice an idempotent operator, so u(r) ≡ 0. This is why ρ(r,r′) has to be generated from a CI wave function.
37. For singlet wave functions, Mulliken atomic populations of u(r) are identical with Mayer's free valences: (a) Mayer, I. Int. J. Quantum Chem. 1986, 29, 73-84. (b) Mayer, I. Int. J. Quantum Chem. 1986, 29, 477-483.
38. For singlet wave functions, Mulliken atomic populations of u(r) are identical with Mayer's free valences: (a) Mayer, I. Int. J. Quantum Chem. 1986, 29, 73-84. (b) Mayer, I. Int. J. Quantum Chem. 1986, 29, 477-483.
39. -/10 orbital CASSCF wave function which includes contributions from the two nodal cyano groups. In the extended CASSCF description, Mulliken populations of effectively unpaired electrons on the CN groups are no longer negligible, as expected due to the naturally large correlation effects in the CN group itself. Nevertheless, despite the marked increase of the total number of effectively unpaired electrons as a result of enlarging the CAS, the populations on the ring carbons exhibit very small changes (see the Supporting Information).
40. (a) Davidson, E. R. Int. J. Quantum Chem. 1998, 69, 241-245.
41. (b) Davidson, E. R. Chem. Phys. Lett. 1998, 284, 301-307.
42. The CASSCF wave function includes all the important configurations needed to describe the PES for the Cope rearrangement, but lacks correlation between the active and inactive electrons (i.e. dynamic correlation). For pericyclic reactions, inclusion of dynamic correlation is necessary to obtain qualitatively correct PES: Borden, W. T.; Davidson, E. R. Acc. Chem. Res. 1996, 29, 67-75. The CASSCF wave function is still an excellent reference state for perturbation theory calculations.
43. Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623-11627.
44. Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100.
45. Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.