Abstract
The mechanistic pathway of singlet bromocarbenes (1CHBr and 1CBr2) insertions into the C-H bonds of methane and ethane have been analysed at ab initio (HF and MP2) and DFT (B3LYP) level of theories using 6-31g (d, p) basis set. The QCISD//MP2/6-31g(d, p) level predicts higher activation barriers. NPA, Mulliken and ESP charge analyses have been carried out along the minimal reaction path by the IRC method at B3LYP and MP2 levels for these reactions. The occurrence of the TSs either in the electrophilic or nucleophilic phase and net charge flow from alkane to carbene in the TS has been identified through NBO analyses.
Chapter PDF
Similar content being viewed by others
References
Irikura, K., Goddard, K., Beauchamp, W.A., Am, J.L.: J. Am. Chem. Soc. 114, 48 (1992)
Kirmse, W.: Carbene Chemistry, 2nd edn. Academic Press, New York (1971)
Fischer, E.O., Maasbol, A.: Angew. Chem. (Int. Ed. Engl.) 3, 580 (1964)
Salaun, J.: Chem. Rev. 89, 1247 (1989)
Brookhart, M., Studabaker, W.B.: Chem. Rev. 87, 411 (1987)
Walbrick, J.M., Wilson, J.W., Jones, W.M.: J. Am. Chem. Soc. 90, 2895 (1968)
Padwa, A., Hornbuckle, S.F.: Chem. Rev. 91, 263 (1991)
Baldvin, J.E., Jesudason, C.D., Moloney, M., Morgan, D.R., Pratt, A.J.: Tetrahedron 47, 5603 (1991)
Von, W., Doering, E., Prinzbach, H.: Tetrahedron 6, 24 (1959)
Russon, N., Siclia, E., Toscano, M.: J. Chem. Phys. 97, 5031 (1992)
Dobson, R.C., Hayes, D.M., Hoffmann, R.: J. Am.Chem. Soc. 93, 6188 (1971)
Fukui, K.: J. Phys. Chem. 74, 4161 (1970)
Gaussian 03, Revision C.02, Gaussian, Inc., Wallingford CT (2004)
Lee, C., Yang, W., Parr, R.G.: Physical Review B 37, 785 (1988)
Becke, D.: Phys. Rev. A 38, 3098 (1988)
Miehlich, B., Savin, A., Stoll, H., Preuss, H.: Chem. Phys. Lett. 157, 200 (1989)
Becke, A.D.: J. Chem. Phys. 98, 5648 (1993)
Becke, A.D.: J. Chem. Phys. 104, 1040 (1996)
Franel, M.M., Pietro, W.J., Hehre, W.J., Bimcley, J.S., Gordon, M.S., DeFrees, D.J., Pople, J.A.: J. Chem. Phys. 77, 3654 (1982)
Hariharan, P.C., Pople, J.A.: Chem. Phys. Lett. 66, 217 (1972)
Pople, J.A., Gordon, M.H., Raghavachari, K.J.: Chem. Phys. 87, 5968 (1987)
Schaftenaar, G., Noordik, J.H.: J. Comput. Aid. Mol. Design 14, 123 (2000)
Gonzalez, C., Schlegel, H.B.: J. Chem. Phys. 94, 5523 (1990)
Mulliken, R.S.: J. Chem. Phys. 23, 1833 (1955)
Reed, A.E., Carpenter, J.E., Weinhold, F., Curtiss, L.A.: Chem. Rev. 88, 8991 (1988)
Breneman, C.M., Wiberg, K.B.: J. Comput. Chem. 11, 361 (1990)
Ramalingam, M., Ramasami, K., Venuvanalingam, P., Sethuraman, V.: J. Mol. Struct (Theochem) 755, 169 (2005)
Bach, R.D., Andres, J.L., Su, M.D., McDouall, J.J.W.: J. Am. Chem. Soc. 115, 5768 (1993)
Gilles, M.K., Lineberger, W.C., Ervin, K.M.: J. Am. Chem. Soc 115, 1031 (1993)
Glendening, E.D., Reed, A.E., Carpenter, J.E., Weinhold, F., Curtiss, L.: Chem. Rev. 3, 899, NB Version 3.1 (1988)
Carpenter, J.E.: Ph.D. Thesis, University of Wisconsin, Madison, WI (1987)
Hammond, G.S.: J. Am. Chem. Soc. 77, 334 (1955)
Author information
Authors and Affiliations
Editor information
Rights and permissions
Copyright information
© 2007 Springer Berlin Heidelberg
About this paper
Cite this paper
Ramalingam, M., Ramasami, K., Venuvanalingam, P., Swaminathan, J. (2007). Ab Initio and DFT Investigations of the Mechanistic Pathway of Singlet Bromocarbenes Insertion into C-H Bonds of Methane and Ethane. In: Shi, Y., van Albada, G.D., Dongarra, J., Sloot, P.M.A. (eds) Computational Science – ICCS 2007. ICCS 2007. Lecture Notes in Computer Science, vol 4488. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-540-72586-2_41
Download citation
DOI: https://doi.org/10.1007/978-3-540-72586-2_41
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-540-72585-5
Online ISBN: 978-3-540-72586-2
eBook Packages: Computer ScienceComputer Science (R0)