The Strain Energy of Perchlorocyclopropane is Small: It Might even be Negative. A Density Functional Theory Study of Perhalocycloalkanes

International Journal of Quantum Chemistry

Volumn 95, Issue 6, 2003, Pages 784-790

  Mahavadi, Madhavi ^a   Zeiger, Diana N ^a   Naqib, Dahlia ^b   Roux, Maria Victoria ^b   Notario, Rafael ^b   Liebman, Joel F ^a  

^a UNIVERSITY OF MARYLAND BALTIMORE COUNTY   (United States)

^b INSTITUTO DE QUÍMICA FÍSICA ROCASOLANO   (Spain)

Author keywords

Density functional theory; Enthalpy of formation; Perhalocycloalkanes; Perhalocyclopropanes; Strain energy

Indexed keywords

CHLORINE COMPOUNDS; ENTHALPY; PROBABILITY DENSITY FUNCTION; PROPANE; STRAIN;

STRAIN ENERGY;

PARAFFINS;

EID: 0242582182     PISSN: 00207608     EISSN: None     Source Type: Journal    
DOI: 10.1002/qua.10585     Document Type: Article

References (31)

1. There are numerous volumes on conformational analysis in which six-membered rings have played a major role. For three-membered rings, there are the multiple volumes in the "Patai series": Rappoport, Z., ed. The Chemistry of the Cyclopropyl Group; Wiley: Chichester, UK; vol. 1, 1987; vol. 2, 1995. A corresponding volume in this series on four-membered rings is in preparation, edited by Z. Rappoport and J. F. Liebman.
2. See, e.g., in the above cyclopropyl vol. 1 the chapter by Liebman, J. F. ; Greenberg, A., p 1083; in vol. 2 the chapter by Liebman, J. F., p 223; and the interpolating study by Liebman, J. F.; Greenberg, A. Chem Rev 1989, 89, 1225.
3. Bernett, W. A. J Org Chem 1969, 34, 1772.
4. Liebman, J. F.; Dolbier, W. R., Jr.; Greenberg, A. J Phys Chem 1986, 90, 394.
5. See, e.g., Seminario, E. D., ed. Recent Developments of Modern Density Functional Theory, Theoretical and Computational Chemistry, vol. 4; Elsevier: Amsterdam, 1996.
6. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986.
7. For a recent quantum chemical (orbital based, Hartree-Fock) study of perfluoro- (and lesser fluorinated) cyclopropane, see Zeiger, D. N.; Liebman, J. F. J Mol Struct 2000, 556, 83. Strain energy for cyclopropane, for fluorinated species, and in general is discussed at length in Greenberg, A.; Liebman, J. F. Strained Organic Molecules; Academic Press: New York, 1978. Archival values are given for the strain energies of cyclopropane and bigger cycloalkanes: As will be noted here, these values are essentially independent of how they were obtained.
8. For a recent quantum chemical (orbital based, Hartree-Fock) study of perfluoro- (and lesser fluorinated) cyclopropane, see Zeiger, D. N.; Liebman, J. F. J Mol Struct 2000, 556, 83. Strain energy for cyclopropane, for fluorinated species, and in general is discussed at length in Greenberg, A.; Liebman, J. F. Strained Organic Molecules; Academic Press: New York, 1978. Archival values are given for the strain energies of cyclopropane and bigger cycloalkanes: As will be noted here, these values are essentially independent of how they were obtained.
9. For a recent article that addresses some calorimetric and conceptual difficulties of fluorinated species within the context of cyclopropane derivatives, see Roux, M. V.; Notario, R.; Zeiger, D. N.; Liebman, J. F. J Fluor Chem 2001, 112, 91.
10. 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.; Burnt, J. C.; Dapprich, S.; Millam, J. M.; Daniels, J. A.; Kudin, K. N.; Strain, M. C.; Parkas, O.; Tomasi, J.; Barone, V.; Petersson, M. 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.; Baboul, A. G.; Martin, B.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.9; Gaussian, Inc.: Pittsburgh, PA, 1998.
11. We used the 6-311G(d) basis set for structure optimization (harmonic frequency) zero-point, and thermal corrections (McLean, A. D.; Chandler, G. S. J Chem Phys 1980, 72, 5639; Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J Chem Phys 1980, 72, 650) and the 6-311+G(2df,p) basis set for single-point energy calculations (Clark, T.; Chandresekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J Comput Chem 1984, 4. 294). We used the B3P86 DFT approach, i.e., Becke's three-parameter functional with the nonlocal correlation provided by the Perdew 86 expression: Becke, A. D. J Chem Phys 1993, 98, 5648; Perdew, J. P. Phys Rev B 1986, 33, 8822.
12. We used the 6-311G(d) basis set for structure optimization (harmonic frequency) zero-point, and thermal corrections (McLean, A. D.; Chandler, G. S. J Chem Phys 1980, 72, 5639; Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J Chem Phys 1980, 72, 650) and the 6-311+G(2df,p) basis set for single-point energy calculations (Clark, T.; Chandresekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J Comput Chem 1984, 4. 294). We used the B3P86 DFT approach, i.e., Becke's three-parameter functional with the nonlocal correlation provided by the Perdew 86 expression: Becke, A. D. J Chem Phys 1993, 98, 5648; Perdew, J. P. Phys Rev B 1986, 33, 8822.
13. We used the 6-311G(d) basis set for structure optimization (harmonic frequency) zero-point, and thermal corrections (McLean, A. D.; Chandler, G. S. J Chem Phys 1980, 72, 5639; Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J Chem Phys 1980, 72, 650) and the 6-311+G(2df,p) basis set for single-point energy calculations (Clark, T.; Chandresekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J Comput Chem 1984, 4. 294). We used the B3P86 DFT approach, i.e., Becke's three-parameter functional with the nonlocal correlation provided by the Perdew 86 expression: Becke, A. D. J Chem Phys 1993, 98, 5648; Perdew, J. P. Phys Rev B 1986, 33, 8822.
14. We used the 6-311G(d) basis set for structure optimization (harmonic frequency) zero-point, and thermal corrections (McLean, A. D.; Chandler, G. S. J Chem Phys 1980, 72, 5639; Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J Chem Phys 1980, 72, 650) and the 6-311+G(2df,p) basis set for single-point energy calculations (Clark, T.; Chandresekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J Comput Chem 1984, 4. 294). We used the B3P86 DFT approach, i.e., Becke's three-parameter functional with the nonlocal correlation provided by the Perdew 86 expression: Becke, A. D. J Chem Phys 1993, 98, 5648; Perdew, J. P. Phys Rev B 1986, 33, 8822.
15. We used the 6-311G(d) basis set for structure optimization (harmonic frequency) zero-point, and thermal corrections (McLean, A. D.; Chandler, G. S. J Chem Phys 1980, 72, 5639; Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J Chem Phys 1980, 72, 650) and the 6-311+G(2df,p) basis set for single-point energy calculations (Clark, T.; Chandresekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J Comput Chem 1984, 4. 294). We used the B3P86 DFT approach, i.e., Becke's three-parameter functional with the nonlocal correlation provided by the Perdew 86 expression: Becke, A. D. J Chem Phys 1993, 98, 5648; Perdew, J. P. Phys Rev B 1986, 33, 8822.
16. Wiberg, K. B. J Org Chem 1999, 64, 6387.
17. George, P.; Trachtman, M.; Bock, C. M.; Brett, A. M. Tetrahedron 1976, 32, 317. See also Dill, J. D.; Greenberg, A.; Liebman, J. F. J Am Chem Soc 1979, 101, 6814. The reader is also addressed to the related isodesmic reasoning study on the quantum chemically calculated enthalpies of formation of the whole set of partially and perfluorinated and -chlorinated cyclopropanes, Novak, I. J Org Chem 2002, 67, 6279.
18. George, P.; Trachtman, M.; Bock, C. M.; Brett, A. M. Tetrahedron 1976, 32, 317. See also Dill, J. D.; Greenberg, A.; Liebman, J. F. J Am Chem Soc 1979, 101, 6814. The reader is also addressed to the related isodesmic reasoning study on the quantum chemically calculated enthalpies of formation of the whole set of partially and perfluorinated and -chlorinated cyclopropanes, Novak, I. J Org Chem 2002, 67, 6279.
19. George, P.; Trachtman, M.; Bock, C. M.; Brett, A. M. Tetrahedron 1976, 32, 317. See also Dill, J. D.; Greenberg, A.; Liebman, J. F. J Am Chem Soc 1979, 101, 6814. The reader is also addressed to the related isodesmic reasoning study on the quantum chemically calculated enthalpies of formation of the whole set of partially and perfluorinated and -chlorinated cyclopropanes, Novak, I. J Org Chem 2002, 67, 6279.
20. All cited strain energies derived from experimentally measured enthalpies of formation arise from taking archival values for the latter from Pedley, J. B.; Naylor, R. D.; Kirby, S. P. Thermochemical Data of Organic Compounds, 2nd ed.; Chapman & Hall: New York, 1986.
21. Atkinson, B.; McKeegan, D. Chem Commun 1966, 189; Bomse, D. S.; Berman, D. W.; Beauchamp, J. L. J Am Chem Soc 1981, 103, 3967.
22. Atkinson, B.; McKeegan, D. Chem Commun 1966, 189; Bomse, D. S.; Berman, D. W.; Beauchamp, J. L. J Am Chem Soc 1981, 103, 3967.
23. However rare, negative strain energies are not unknown, e.g., [6,6]-paracyclophane so qualifies; cf. Shieh, C.-F.; McNally, D.; Boyd, R. H. Tetrahedron 1969, 25, 3653.
24. See, e.g., Benson, S. W.; Buss, J. H. J Chem Phys 1958, 29, 546; Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. W. J Am Chem Soc 1971, 93, 1637; Engler, E. M.; Andose, J. D.; Schleyer, P. v. R. J Am Chem Soc 1973, 95, 8005.
25. See, e.g., Benson, S. W.; Buss, J. H. J Chem Phys 1958, 29, 546; Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. W. J Am Chem Soc 1971, 93, 1637; Engler, E. M.; Andose, J. D.; Schleyer, P. v. R. J Am Chem Soc 1973, 95, 8005.
26. See, e.g., Benson, S. W.; Buss, J. H. J Chem Phys 1958, 29, 546; Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. W. J Am Chem Soc 1971, 93, 1637; Engler, E. M.; Andose, J. D.; Schleyer, P. v. R. J Am Chem Soc 1973, 95, 8005.
27. Van Vechten, D.; Liebman, J. F. Isr J Chem 1981, 21, 105; Liebman, J. F. ; Van Vechten, D. In: Liebman, J. F.; Greenberg, A., eds. Molecular Structure and Energetics: Physical Measurements, vol. 2; VCH Publishers: New York, 1987; p 315-374.
28. Van Vechten, D.; Liebman, J. F. Isr J Chem 1981, 21, 105; Liebman, J. F. ; Van Vechten, D. In: Liebman, J. F.; Greenberg, A., eds. Molecular Structure and Energetics: Physical Measurements, vol. 2; VCH Publishers: New York, 1987; p 315-374.
29. Skancke, A.; Van Vechten, D.; Liebman, J. F.; Skancke, P. N. J Mol Struct 1996, 376, 461.
30. 3(XYZ).
31. m for cyclohexane, dodecahedrane, and the so-called [60]fullerane as well as discussing related perfluorinated and perbrominated species.