Bulletin of the Korean Chemical Society

  • 제31권3호
  • /
  • Pages.595-598
  • /
  • 2010
  • /
  • 0253-2964(pISSN)
  • /
  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
권호 표지
DOI QR코드

DOI QR Code

Reactions of Acetyl Radical with Acetylene - A Computational Study

  • Tran, Tu Anh (School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne) ;
  • Schiesser, Carl H. (School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne)
  • 발행 : 2010.03.20
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

Ab initio and DFT molecular orbital calculations predict that acetyl radical reacts with acetylene through interactions primarily involving the SOMO of the radical and the in-plane ${\pi}$-bond of acetylene. An energy barrier (${\Delta}E_1$) of 39.6 kJ $mol^{-1}$ is predicted for the preferred anti arrangement of reactants at the CCSD(T)/cc-pVDZ//BHandHLYP/cc-pVDZ level of theory. NBO analysis reveals additional interactions between the radical SOMO and the nearby C-H ${\sigma}$-bond in acetylene worth about 10% of the total transition state interaction energy. This type of orbital interaction has not previously been observed in radical addition reactions involving C-C ${\pi}$-bonds.

키워드

참고문헌

  1. Lucas, M. A.; Schiesser, C. H. J. Org. Chem. 1996, 61, 5754 https://doi.org/10.1021/jo960838y
  2. Lucas,M. A.; Schiesser, C. H. J. Org. Chem. 1998, 63, 3032 https://doi.org/10.1021/jo9722111
  3. Schiesser,C. H.; Skidmore, M. A. J. Org. Chem. 1998, 63, 5713. https://doi.org/10.1021/jo980710b
  4. Chatgilialoglu, C.; Crich, D.; Komatsu, M.;Ryu, I. Chem. Rev. 1999, 99, 1991 https://doi.org/10.1021/cr9601425
  5. Crich, D.; Chen, C.; Hwang, J.-T.; Papadatos, A.; Walter, R. I. J. Am. Chem. Soc. 1994, 116, 8937. https://doi.org/10.1021/ja00099a011
  6. Schiesser, C, H.; Wille, U.; Matsubara, H.; Ryu,I. Acc. Chem. Res. 2007, 40, 303 https://doi.org/10.1021/ar600015v
  7. Baldwin, J. E. J. Chem. Soc. Chem. Commun. 1976, 734.
  8. Kyne, S. H.; Schiesser, C. H.; Matsubara, H. J. Org. Chem. 2008,73, 427. https://doi.org/10.1021/jo701825y
  9. Schiesser, C. H.; Matsubara, H.; Ritsner, I.; Wille, U. Chem. Commun.2006, 1067
  10. Matsubara, H.; Falzon, C. T.; Ryu, I.; Schiesser,C. H. Org. Biomol. Chem. 2006, 4, 1920 https://doi.org/10.1039/b603024f
  11. Kyne, S. H.; Schiesser, C.H. Org. Biomol. Chem. 2007, 5, 3938 https://doi.org/10.1039/b714324a
  12. Kyne, S. H.; Schiesser, C. H.Aust. J. Chem. 2009, 62, 728 https://doi.org/10.1071/CH09165
  13. Horvat, S. M.; Schiesser, C. H. Organometallics2009, 28, 3311 https://doi.org/10.1021/om801016x
  14. Amos, R. I. J.; Smith, J. A.; Yates, B.F. Tetrahedron 2009, 65, 7653. https://doi.org/10.1016/j.tet.2009.06.102
  15. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,M. A.; Cheeseman, J. R.; Montgomery, J. A.; Vreven, Jr.,T.; Kudin,K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Borone,V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Peterson,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.;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. G.; Chen, W.; Wong, M. W.; Gonzalez, C. J.; Pople,A.; Gaussian 03, Revision B. 05; Gaussian Inc., Pittsburgh, PA,2003.
  16. Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.;Bohmann, J. A.; Morales, C. M.; Weinhold, F. NBO 5.0; Theoretical Chemical Institute: University of Wisconsin, Madison, WI,2001.
  17. Radom, L. Aust. J. Chem. 1975, 28, 1. https://doi.org/10.1071/CH9750001
  18. Simon, S.; Duran, M.; Dannenberg, J. J. J. Chem. Phys. 1996, 105,11024 https://doi.org/10.1063/1.472902
  19. Boys, S. F.; Bernardi, F. Mol. Phys. 1970, 19, 553. https://doi.org/10.1080/00268977000101561