Browse > Article
http://dx.doi.org/10.5012/jkcs.2006.50.4.291

Ab initio and DFT Study for the Internal Rotations of Cyclopropyldifluoroborane Molecule  

Kim, Gyeong-Lee (서일대학)
Lee, Jeong-Gyeong (한국기초과학지원연구원)
Publication Information
Journal of the Korean Chemical Society / v.50, no.4, 2006 , pp. 291-297 More about this Journal
Abstract
The equilibrium structures, relative energies and NBO analyses for the possible conformations and transition states which can exist on the internal rotation of CPDFB and CPCFB molecules have been investigated using DFT and ab initio methods with various basis sets. The interaction between bonding orbital ((C1-C3, C2-C3)) and antibonding orbital (n*(B9) and *(B9-Cl11)) was the main characteristic hyperconjugation in both molecules. In addition, the stabilization energy of CPDFB was 6.63kcal/mol and that of CPCFB was 6.97(E-form)/6.79(Z-form) kcal/mol for each conformation. The rotational barriers by internal rotation of BF2- and BFCl- functional groups were evaluated to be 5.3~6.7kcal/mol and 5.7~6.5kcal/mol respectively, which showed good agreement with the experimental values reported by previous dynamic NMR study. Finally, Z-form was more stable than E-form by 0.2 kcal/mol in CPCFB molecule and therefore Z-form was confirmed as global minimum.
Keywords
Cyclopropyl; Hyperconjugation; Rotational Barrier; DFT; Ab initio
Citations & Related Records

Times Cited By SCOPUS : 0
연도 인용수 순위
  • Reference
1 Durig, J. R.; Carter, R. O.; Odom, J. D.; Inorg. Chem. 1974, 13, 701   DOI
2 Gordon, M. H.; Pople, J. A.; Frisch, M. J., Chem. Phys. Lett. 1988, 153, 503   DOI   ScienceOn
3 Odom, J. D.; Szafran, Z.; Johnston, S. A.; Li, Y. S.; Durig, J. R.; J. Am. Chem. Soc. 1980, 102, 7173   DOI
4 Foster J. P.; Weinhold F., J. Am. Chem. Soc. 1980, 102, 7211   DOI
5 Hoffmann, R. Tetrahderon Lett. 1965, 43, 3819
6 Gaussian 03, Revision C.02, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; 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.; Gonzalez, C.; and Pople, J. A.; Gaussian, Inc., Wallingford CT, 2004
7 Cremer, D.; Kraka, E., J. Am. Chem. Soc. 1985, 107, 3811   DOI
8 Yirong, M.; Schleyer, P. R.; Jiao, H.; Lin, Z., Chem. Phys. Lett. 1997, 280, 439   DOI   ScienceOn
9 Haywood- Farmer, J. Chem. Rev., 1974, 74, 315   DOI
10 de Meijere, A., Angew. Chem., Int. Ed. Engl. 1979, 18, 809   DOI   ScienceOn
11 Roberts, J. D.; Mazur, R. H., J. Am. Chem. Soc., 1951, 73, 2509   DOI
12 Eastman, R. H.; Freeman, S. K., J. Am. Chem. Soc. 1955, 77, 6642   DOI
13 Pittman, C. U.; Olah, G. A., J. Am. Chem. Soc. 1965, 87, 5123   DOI
14 Walsh, A. D., Trans. Faraday Soc. 1949, 49, 179
15 Hoffman, R., J. Chem. Phys. 1964, 40, 2480   DOI
16 Bernett, W. A., J. Chem. Educ. 1967, 44, 17   DOI
17 Clark, T.; Spitznagel, G. W.; Klose, R.; Schleyer, P. R., J. Am. Chem. Soc. 1984, 106, 4412   DOI
18 Eric, A. N.; Rose, M. Y.; J. Am. Chem. Soc. 1982, 104, 6218-6220   DOI
19 Pawar, D. M.; Parks, R.; Price, M.; Reese, D.; Noe, E. A.; J. Mol. Struct. 2000, 525, 209   DOI   ScienceOn
20 Kabakoff, D. S.; Namanworth, E.; J. Am. Chem. Soc. 1970, 92, 3234   DOI
21 Pawar, D. M.; Noe, E. A., J. Org. Chem. 1998, 63, 2850   DOI   ScienceOn
22 Durig, J. R.; Hall, L. W.; Carter, R. O.; Wurrey, C. J.; kalasinsky, V. F.; Odom, J. D., J. Phys. Chem. 1976, 80, 1188   DOI
23 Christen, D.; Lister, D.; Sheridan J., J. Chem. Soc. 1960, 82, 6218   DOI
24 Becke, A. D., J. Chem. Phys. 1993, 98, 5648   DOI   ScienceOn
25 Gonzalez, C.; Schlegel, H. B., J. Chem. Phys. 1989, 90, 2154   DOI
26 Gonzalez, C.; Schlegel, H. B., J. Phys. Chem. 1990, 94, 5523   DOI
27 Cances, M. T.; Mennucci, B.; Tomasi, J., J. Chem. Phys. 1997, 107, 3032   DOI   ScienceOn