Variable Trends in R-X Bond Dissociation Energies (R = Me, Et, i-Pr, t-Bu)

Organic Letters

Volumn 5, Issue 24, 2003, Pages 4689-4692

  Coote, Michelle L ^a   Pross, Addy ^b   Radom, Leo ^c  

^a AUSTRALIAN NATIONAL UNIVERSITY   (Australia)

^b BEN GURION UNIVERSITY OF THE NEGEV   (Israel)

^c UNIVERSITY OF SYDNEY   (Australia)

Author keywords

[No Author keywords available]

Indexed keywords

AB INITIO CALCULATION; ARTICLE; CHEMICAL BOND; DISSOCIATION; ENERGY; MOLECULAR DYNAMICS; QUALITATIVE ANALYSIS;

EID: 0346150271     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol035860+     Document Type: Article

References (14)

1. See, for example: March, J. Advanced Organic Chemistry: Reactions, Mechanisms and Structure; McGraw-Hill: New York, 1963; p 153.
2. Benson, S. W.; Shaw, R. Adv. Chem. Ser. 1968, 75, 287-294.
3. Rüchardt, C. Angew. Chem., Int. Ed. Engl. 1970, 9, 830-843.
4. Zavitsas, A. A. J. Chem. Educ. 2001, 78, 417-419.
5. Matsunaga, N.; Rogers, D. W.; Zavitsas, A. A. J. Org. Chem. 2003, 68, 3158-3172.
6. Standard ab initio molecular orbital calculations were performed using the GAUSSIAN 98 and MOLPRO 2000.6 software packages: (a) 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.; 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; Gaussian, Inc.: Pittsburgh, PA, 1998. (b) Werner, H.-J.; Knowles, P. J.; Amos, R. D.; Bernhardsson, A.; Berning, A.; Celani, P.; Cooper, D. L.; Deegan, M. J. O.; Dobbyn, A. J.; Eckert, F.; Hampel, C.; Hetzer, G.; Korona, T.; Lindh, R.; Lloyd, A. W.; McNicholas, S. J.; Manby, F. R.; Meyer, W.; Mura, M. E.; Nicklass, A.; Palmieri, P.; Pitzer, R.; Rauhut, G.; Schütz, M.; Stoll, H.; Stone, A. J.; Tarroni, R.; Thorsteinsson, T. MOLPRO 2000.6; University of Birmingham: Birmingham, 1999.
7. Standard ab initio molecular orbital calculations were performed using the GAUSSIAN 98 and MOLPRO 2000.6 software packages: (a) 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.; 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; Gaussian, Inc.: Pittsburgh, PA, 1998. (b) Werner, H.-J.; Knowles, P. J.; Amos, R. D.; Bernhardsson, A.; Berning, A.; Celani, P.; Cooper, D. L.; Deegan, M. J. O.; Dobbyn, A. J.; Eckert, F.; Hampel, C.; Hetzer, G.; Korona, T.; Lindh, R.; Lloyd, A. W.; McNicholas, S. J.; Manby, F. R.; Meyer, W.; Mura, M. E.; Nicklass, A.; Palmieri, P.; Pitzer, R.; Rauhut, G.; Schütz, M.; Stoll, H.; Stone, A. J.; Tarroni, R.; Thorsteinsson, T. MOLPRO 2000.6; University of Birmingham: Birmingham, 1999.
8. An assessment of the reliability of this level of theory can be found in: Henry, D. J.; Parkinson, C. J.; Radom, L. J. Phys. Chem. A 2002, 106, 7927-7936.
9. Unless otherwise noted, IEs and EAs were calculated at a modified G3(MP2)-RAD level of theory, G3(MP2)-RAD(+), in which the URCCSD-(T) and corresponding RMP2 calculations are performed with the 6-31+G-(d) basis set instead of the normal 6-31G(d) basis set.
10. Coote, M. L.; Radom, L. Macromolecules. Submitted for publication.
11. Pross, A. Theoretical and Physical Principles of Organic Reactivity; John Wiley & Sons: New York, 1995.
12. Situations in which the bond energy is dominated by resonance between the covalent and ionic contributions have been named "charge-shift bonding" by Shaik, Hiberty, and co-workers. For more detailed discussions of this effect, see for example: (a) Shaik, S.; Maitre, P.; Sini, G.; Hiberty, P. C. J. Am. Chem. Soc. 1992, 114, 7861-7866. (b) Galbraith, J. M.; Blank, E.; Shaik, S.; Hiberty, P. C. Chem. Eur. J. 2000, 6, 2425-2434. (c) Shurki, A.; Hiberty, P. C.; Shaik, S. J. Am. Chem. Soc. 1999, 121, 822-834.
13. Situations in which the bond energy is dominated by resonance between the covalent and ionic contributions have been named "charge-shift bonding" by Shaik, Hiberty, and co-workers. For more detailed discussions of this effect, see for example: (a) Shaik, S.; Maitre, P.; Sini, G.; Hiberty, P. C. J. Am. Chem. Soc. 1992, 114, 7861-7866. (b) Galbraith, J. M.; Blank, E.; Shaik, S.; Hiberty, P. C. Chem. Eur. J. 2000, 6, 2425-2434. (c) Shurki, A.; Hiberty, P. C.; Shaik, S. J. Am. Chem. Soc. 1999, 121, 822-834.
14. Situations in which the bond energy is dominated by resonance between the covalent and ionic contributions have been named "charge-shift bonding" by Shaik, Hiberty, and co-workers. For more detailed discussions of this effect, see for example: (a) Shaik, S.; Maitre, P.; Sini, G.; Hiberty, P. C. J. Am. Chem. Soc. 1992, 114, 7861-7866. (b) Galbraith, J. M.; Blank, E.; Shaik, S.; Hiberty, P. C. Chem. Eur. J. 2000, 6, 2425-2434. (c) Shurki, A.; Hiberty, P. C.; Shaik, S. J. Am. Chem. Soc. 1999, 121, 822-834.