Singlet hydrocarbon carbenes with high barriers toward isomerization: A computational investigation

Journal of the American Chemical Society

Volumn 125, Issue 30, 2003, Pages 9070-9073

  Nicolaides, Athanassios ^a  

^a UNIVERSITY OF CYPRUS   (Cyprus)

Author keywords

[No Author keywords available]

Indexed keywords

BOND CLEAVAGE;

CHEMICAL BONDS; GROUND STATE; HYDROGEN; ISOMERIZATION;

NITROGEN COMPOUNDS;

CARBENE; HYDROCARBON;

ARTICLE; CHEMICAL STRUCTURE; ENERGY; GEOMETRY; ISOMERISM; KINETICS; VIBRATION;

EID: 0042868658     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0299699     Document Type: Article

References (47)

1. See, for example: (a) Kirmse, W. In Carbene Chemistry; Academic Press Inc.: New York, 1964,
2. (b) Moss, R. A., Jones, M., Jr., Eds. Carbenes; Wiley: New York, 1973, 1975; Vols I and II.
3. (c) Wentrup, C. In Reactive Molecules; Wiley-Interscience: New York, 1984.
4. (d) Platz, M. S.; Maloney, V. M. In Kinetics and Spectroscopy of Carbenes and Biradicals; Platz, M. S., Ed.; Plenum: New York, 1990.
5. (e) Jones, Jr. M. In Advances in Carbene Chemistry; Brinker, U., Ed.; JAI Press; Greenwich, CT, 1998; Vol. 2, pp 77-96.
6. (f) Platz, M. S. In Advances in Carbene Chemistry; Brinker, U., Ed.; JAI Press; Greenwich, CT, 1998; Vol. 2, pp 132-174.
7. (g) Bertrand, G., Ed.; Carbene Chemistry: From Fleeting Intermediates to Powerful Reagents; Marcel Dekker: Netherlands, 2002.
8. (a) Tomioka, H. Acc. Chem. Res. 1997, 30, 1315.
9. (b) Tomioka, H. In Advances in Carbene Chemistry; Brinker, U., Ed.; JAI Press; Greenwich, CT, 1998; Vol 2, pp 175-214.
10. (c) Tomioka, H.; Watanabe, T.; Hattori, M.; Nomura, N.; Hirai, K. J. Am. Chem. Soc. 2002, 124, 474.
11. (a) Arduengo A. J. Acc. Chem. Res. 1999, 32, 913.
12. (b) Bourissou, D.; Guerret, O.; Gabbai, F. P.; Bertrand, G. Chem. Rev. 2000, 100, 39.
13. (a) Despagnet, E.; Gornitzka, H.; Rozhenko, A. B.; Schoeller, W. W.; Bourissou, D.; Bertrand, G. Angew. Chem., Int. Ed. Engl. 2002, 41, 2835.
14. (b) Sole, S.; Gornitzka, H.; Schoeller, W. W.; Bourissou D.; Bertrand G. Science 2001, 292, 5523.
15. (a) Alder, R. W.; Allen, P. R.; Murra, M.; Orpen, A. G. Angew. Chem., Int. Ed. Engl. 1996, 35, 1121.
16. (b) Alder, R. W.; Butts, C. P.; Orpen, A. G. J. Am. Chem. Soc. 1998, 120, 11 526.
17. (a) Regitz, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 674.
18. (b) Heinemann, C.; Müller, T. Apeloig, Y.; Schwartz, H. J. Am. Chem. Soc. 1996, 118, 2023.
19. (c) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039.
20. 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.; 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, Foresman, J. B.; K.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; 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. W. M.; 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.
21. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
22. (b) Lee, C.; Yang, W.; Parr, G. Phys. Rev. B: Condens. Matter 1988, 37, 785.
23. Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16 502.
24. Baboul, A. G.; Curtiss, L. A.; Redfern, P. C.; Raghavachari, K. J. Chem. Phys. 1999, 110, 7650.
25. McKellar, A. R. W.; Bunker, P. R.; Sears, T. J.; Evenson, K. M.; Saykally, R. J.; Langhoff, S. R. J. Phys. Chem. 1983, 79, 5251.
26. Xu, G.; Chang, T.-M.; Zhou, J.; McKee, M. L.; Shevlin, P. B. J. Am. Chem. Soc. 1999, 121, 7150.
27. 13 in 4.
28. Dialkylcarbenes usually have singlet ground-states. For notable exceptions, see: (a) Gano, J. E.; Wettach, R. H.; Platz, M. S.; Senthilnathan, V. P. J. Am. Chem. Soc. 1982, 104, 2326. (b) Myers, D. R.; Senthilnathan, V. P.; Platz, M. S.; Jones, J., Jr. J. Am. Chem. Soc. 1986, 108, 4232. (c) Iiba, E.; Hirai, K.; Tomioka, H.; Yoshioka, Y. J. Am. Chem. Soc. 2002, 124, 14 308.
29. Dialkylcarbenes usually have singlet ground-states. For notable exceptions, see: (a) Gano, J. E.; Wettach, R. H.; Platz, M. S.; Senthilnathan, V. P. J. Am. Chem. Soc. 1982, 104, 2326. (b) Myers, D. R.; Senthilnathan, V. P.; Platz, M. S.; Jones, J., Jr. J. Am. Chem. Soc. 1986, 108, 4232. (c) Iiba, E.; Hirai, K.; Tomioka, H.; Yoshioka, Y. J. Am. Chem. Soc. 2002, 124, 14 308.
30. Dialkylcarbenes usually have singlet ground-states. For notable exceptions, see: (a) Gano, J. E.; Wettach, R. H.; Platz, M. S.; Senthilnathan, V. P. J. Am. Chem. Soc. 1982, 104, 2326. (b) Myers, D. R.; Senthilnathan, V. P.; Platz, M. S.; Jones, J., Jr. J. Am. Chem. Soc. 1986, 108, 4232. (c) Iiba, E.; Hirai, K.; Tomioka, H.; Yoshioka, Y. J. Am. Chem. Soc. 2002, 124, 14 308.
31. Hehre, W. J.; Radom, L.; Pople, J. A.; Schleyer, P. v. R. Ab Initio Molecular Orbital Theory; John Wiley & Sons: New York, 1986.
32. (a) Sulzbach, H. M.; Platz, M. S.; Schaefer, H. F.; Hadad, M. J. Am. Chem. Soc. 1997, 119, 5682.
33. (b) Kirmse, W.; Meinert, T.; Modarelli, D. A.; Platz, M. S.; J. Am. Chem. Soc. 1993, 115, 8918.
34. (c) Pezacki, J. P.; Pole, D. L.; Warkentin, J. Chen, T.; Ford, F.; Toscano, J.; Fell, J.; Platz, M. S. J. Am. Chem. Soc. 1997, 119, 3191.
35. (d) Stracener, L. L.; Halter, R. J.; McMahon, R. J.; Castro, C.; Karney, W. L. J. Org. Chem. 2000, 65, 199.
36. (e) Dyer, S. F.; Kammula, S.; Shevlin, P. B. J. Am. Chem. Soc. 1977, 99, 8104.
37. (f) Nicolaides, A.; Matshushita, T.; Tomioka, H. J. Org. Chem. 1999, 64, 3299.
38. The singlet states of carbenes 3 and 5 are not expected to have the same stabilization energy, because hyperconjugation in the former case involves C-C bonds, and in the latter C-H bonds.
39. At the B3LYP/6-311+G level of theory, from ref 12.
40. Warner, P. M. Chem. Rev. 1989, 89, 1067.
41. By comparison the length of the CC double bond of the isomeric diradical 22 is 1.32 Å.
42. Out-of-plane β-CC cleavage requires more energy than the in-plane cleavage by 11.6 and 13.6 kcal/mol for 1 and 2, respectively.
43. β is 0.06 Å longer in 1 than in 3 and 4
44. The barrier is less than 0.01 kcal/mol before ZPE correction at the B3LYP/ 6-31G level of theory.
45. (a) Angus, R. O., Jr.; Schmidt, M. W.; Johnson, R. P. J. Am. Chem. Soc. 1985, 107, 532.
46. (b) Bettinger, H. F.; Schreiner, P. R.; Schleyer, P. v. R.; Schaefer, H. F. J. Phys. Chem. 1996, 100, 16 147.
47. Borden, W. T. Chem. Rev. 1989, 89, 1095.