Kinetics and equilibrium constants for reactions of α-phenyl- substituted cyclopropylcarbinyl radicals

Journal of the American Chemical Society

Volumn 122, Issue 13, 2000, Pages 2988-2994

  Halgren, Thomas A ^a,d   Roberts, John D ^b   Horner, John H ^c   Martinez, Felix N ^c   Tronche, Christopher ^c   Newcomb, Martin ^c  

^a MERCK RESEARCH LABORATORIES   (United States)

^b California Institute of Technology   (United States)

^c WAYNE STATE UNIVERSITY   (United States)

^d SCHRÖDINGER INC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BUTANE; CARBONYL DERIVATIVE; CYCLOPROPANE DERIVATIVE; METHANE; NAPHTHALENE DERIVATIVE; PHENYL GROUP; RADICAL;

ARTICLE; CHEMICAL REACTION KINETICS; CYCLIZATION; ENTHALPY; EQUILIBRIUM CONSTANT; PHOTOLYSIS;

EID: 0034607457     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991114h     Document Type: Article

References (57)

1. Halgren, T. A.; Howden, M. E. H.; Medof, M. E.; Roberts, J. D. J. Am. Chem. Soc. 1967, 89, 3051-3052.
2. Halgren, T. A. Ph.D. Thesis, California Institute of Technology, 1968.
3. Bowry, V. W.; Lusztyk, J.; Ingold, K. U. J. Chem. Soc., Chem. Commun. 1990, 923-925.
4. Beckwith, A. L. J.; Bowry, V. W. J. Am. Chem. Soc. 1994, 116, 2710-2716.
5. Walton, J. C. Magn. Reson. Chem. 1987, 25, 998-1000.
6. Martinez, F. N.; Schlegel, H. B.; Newcomb, M. J. Org. Chem. 1996, 61, 8547-8550. Martinez, F. N.; Schlegel, H. B.; Newcomb, M. J. Org. Chem. 1998, 63, 3618-3623.
7. Martinez, F. N.; Schlegel, H. B.; Newcomb, M. J. Org. Chem. 1996, 61, 8547-8550. Martinez, F. N.; Schlegel, H. B.; Newcomb, M. J. Org. Chem. 1998, 63, 3618-3623.
8. Smith, D. M.; Nicolaides, A.; Golding, B. T.; Radom, L. J. Am. Chem. Soc. 1998, 120, 10223-10233.
9. The acronym PTOC is derived from pyridine-2-thioneoxycarbonyl.
10. Barton, D. H. R.; Crich, D.; Motherwell, W. B. Tetrahedron 1985, 47, 3901-3924.
11. For early LFP applications of PTOC esters in kinetic studies, see: Bohne, C.; Boch, R.; Scaiano, J. C. J. Org. Chem. 1990, 55, 5414-5418. Ha, C.; Horner, J.H.; Newcomb, M.; Varick, T. R.; Arnold, B. R.; Lusztyk, J. J. Org. Chem. 1993, 58, 1194-1198.
12. For early LFP applications of PTOC esters in kinetic studies, see: Bohne, C.; Boch, R.; Scaiano, J. C. J. Org. Chem. 1990, 55, 5414-5418. Ha, C.; Horner, J.H.; Newcomb, M.; Varick, T. R.; Arnold, B. R.; Lusztyk, J. J. Org. Chem. 1993, 58, 1194-1198.
13. Falvey, D. E.; Schuster, G. B. J. Am. Chem. Soc. 1986, 108, 7419-7420. Hilborn, J. W.; Pincock, J. A. J. Am. Chem. Soc. 1991, 113, 2683-2686. Bockman, T. M.; Hubig, S. M.; Kochi, J. K. J. Am. Chem. Soc. 1996, 118, 4502-4503.
14. Falvey, D. E.; Schuster, G. B. J. Am. Chem. Soc. 1986, 108, 7419-7420. Hilborn, J. W.; Pincock, J. A. J. Am. Chem. Soc. 1991, 113, 2683-2686. Bockman, T. M.; Hubig, S. M.; Kochi, J. K. J. Am. Chem. Soc. 1996, 118, 4502-4503.
15. Falvey, D. E.; Schuster, G. B. J. Am. Chem. Soc. 1986, 108, 7419-7420. Hilborn, J. W.; Pincock, J. A. J. Am. Chem. Soc. 1991, 113, 2683-2686. Bockman, T. M.; Hubig, S. M.; Kochi, J. K. J. Am. Chem. Soc. 1996, 118, 4502-4503.
16. Alam, M. M.; Watanabe, A.; Ito, O. J. Org. Chem. 1995, 60, 3440-3444.
17. Chatgilialoglu, C. In Handbook of Organic Photochemistry; Scaiano. J. C., Ed.; CRC Press: Boca Raton, FL, 1989; Vol. 2, pp 3-11.
18. Newcomb, M.; Choi, S. Y.; Homer, J. H. J. Org. Chem. 1999, 64, 1225-1231.
19. Effio, A.; Griller, D.; Ingold, K. U.; Beckwith, A. L. J.; Serelis, A. K. J. Am. Chem. Soc. 1980, 102, 1734-1736.
20. Chatgilialoglu, C.; Ingold, K. U.; Scaiano, J. C. J. Am. Chem. Soc. 1981, 103, 7739-7742.
21. (a) Berkowitz, J.; Ellison, G. B.; Gutman, D. J. Phys. Chem. 1994, 98, 2744-2765.
22. (b) McMillen, D. F.; Golden, D. M. Annu. Rev. Phys. Chem. 1982, 33, 493-532.
23. (c) Rossi, M.; McMillen, D. F.; Golden, D. M. J. Phys. Chem. 1984, 88, 5031-5039.
24. The G2 (Gaussian-2) method was found to give a mean absolute error of only 1.3 kcal/mol for a test set of 125 well-characterized energy differences; see: Curtiss, L. A.; Raghavachari, K.; Trucks, G. W.; Pople J. A. J. Phys. Chem. 1990, 94, 7221-7230.
25. Schlegel, H. B. Private communication of unpublished results. We are grateful to Prof. Schlegel for providing us with this information.
26. The structure of 1 was originally computed by Prof. K. N. Houk and D. Sawicka to whom we are grateful: Houk, K. N.; private communication to JDR 1998.
27. CRC Handbook of Chemistry and Physics. 79th ed.; Lide, D. R., Ed.; CRC Press: Boca Raton, 1998; pp 5-5 to 5-60.
28. Thermochemical estimates vary considerably. For example, Fischer and co-workers used measured and assumed values for BDEs and heats of formation to estimate the exothermicities of methyl radical additions to alkenes. Comparisons between (i) additions to ethene and styrene and (ii) additions to styrene and 1,1-diphenylethene are germane to the thermochemistry we are attempting to address. Differences of 10.7 and 2.5 kcal/ mol for processes i and ii, respectively, were reported in 1995 (Wu, J. Q.; Fischer, H. Int. J. Chem. Kinet. 1995, 27, 167-179). in good agreement with the thermochemical differences we discuss. In ref 24. however, the same differences were listed as 11.7 and 7.9 kcal/mol. respectively. The latter value appears to be out of line; it can be traced mainly to a difference of about 6 kcal/mol in the estimated values for the heat of formation of 1,1-diphenylethene used in the two works.
29. Zytowski, T.; Fischer, H. J. Am. Chem. Soc. 1997, 119, 12869-12878.
30. Friesner, R. A.; Murphy, R. B.; Beachy, M. D.; Ringnalda, M. N.; Pollard, W. T.; Dunietz, B. D.; Cao, Y. J. Phys. Chem. A 1999, 103, 1913-1928. Beachy, M. D. Ph.D. Thesis, Columbia University. 1998. Murphy, R. B.; Pollard, W. T.; Friesner, R. A. J. Chem. Phys. 1997, 106, 5073-5084.
31. Friesner, R. A.; Murphy, R. B.; Beachy, M. D.; Ringnalda, M. N.; Pollard, W. T.; Dunietz, B. D.; Cao, Y. J. Phys. Chem. A 1999, 103, 1913-1928. Beachy, M. D. Ph.D. Thesis, Columbia University. 1998. Murphy, R. B.; Pollard, W. T.; Friesner, R. A. J. Chem. Phys. 1997, 106, 5073-5084.
32. Friesner, R. A.; Murphy, R. B.; Beachy, M. D.; Ringnalda, M. N.; Pollard, W. T.; Dunietz, B. D.; Cao, Y. J. Phys. Chem. A 1999, 103, 1913-1928. Beachy, M. D. Ph.D. Thesis, Columbia University. 1998. Murphy, R. B.; Pollard, W. T.; Friesner, R. A. J. Chem. Phys. 1997, 106, 5073-5084.
33. Newcomb, M. Tetrahedron 1993, 49, 1151-1176.
34. Wong, M. W.; Radom, L. J. Phys. Chem. A 1998, 102, 2237-2245.
35. We thank Prof. H. B. Schlegel, Wayne State University, for pointing out this factor.
36. Newcomb, M.; Tanaka, N.; Bouvier, A.; Tronche, C.; Horner, J. H.; Musa, O. M.; Martinez, F. N. J. Am. Chem. Soc. 1996, 118, 8505-8506.
37. Horner, J. H.; Tanaka, N.; Newcomb, M. J. Am. Chem. Soc. 1998, 120, 10379-10390.
38. Furxhi, E.; Horner, J. H.; Newcomb, M. J. Org. Chem. 1999, 64, 4064-4068.
39. Horner, J. H.; Lakshmipathy, G.; Newcomb, M. Unpublished results.
40. Chatgilialoglu, C.; Newcomb, M. In Advances in Organometallic Chemistry; West, R., Hill, A. F., Eds.; Academic: San Diego, 1999; Vol. 44, pp 67-112.
41. Esker, J. L.; Newcomb, M. J. Org. Chem. 1993, 4933-4940.
42. Graham, S. H.; Williams, J. S. J. Chem. Soc. 1959, 4066-4073.
43. Tokuda, M.; Miyamoto, T.; Fujita, H.; Suginome, H. Tetrahedron 1991, 47, 747-756.
44. Silbert, L. S.; Swern, D. Anal. Chem. 1958, 30, 385-387.
45. Howden, M. E. H. Ph.D. Thesis, California Institute of Technology, 1962.
46. Kriegsmann, H.; Ulbricht, K. Z. Anorg. Chem. 1964, 328, 90-104.
47. Jaguar, version 3.5; Schrödringer Inc.: Portland, OR 97204.
48. Gaussian 94 (Revision E.2); 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, Inc.; Pittsburgh PA, 1995.
49. Gaussian 98 (Revision A.6); Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kundin, 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. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A.; Gaussian, Inc.: Pittsburgh, PA, 1998.
50. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
51. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
52. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory, Wiley: New York, 1986, Chapter 4.
53. Pople, J. A.; Nesbet, R. K. J. Chem. Phys. 1954, 22, 571-572.
54. Here, cc-pVTZ(-f) refers to the triple-ζ correlation-consistent basis set of Dunning, excluding f functions on second-row elements and d functions on hydrogen; see: Dunning, T. H. J. Chem. Phys. 1989, 90, 1007-1023.
55. Krishnan, R.; Frisch, M. J.; Pople J. A. J. Chem. Phys. 1980, 72, 4244-4245. Krishnan, R.; Pople, J. A. Int. J. Quantum Chem. 1978, 14, 91-100.
56. Krishnan, R.; Frisch, M. J.; Pople J. A. J. Chem. Phys. 1980, 72, 4244-4245. Krishnan, R.; Pople, J. A. Int. J. Quantum Chem. 1978, 14, 91-100.
57. Schlegel, H. B. J. Chem. Phys. 1986, 84, 4530.