Abstract
The mechanism of the cycloadditional reaction between singlet dichloro-germylidene(R1) and (acetaldehyde(R2) has been investigated with MP2/6-31G* method, including geometry optimization, vibrational analysis and energies for the involved stationary points on the potential energy surface. From the potential energy profile, we predict that the cycloaddition reaction between singlet dichloro-germylidene and acetaldehyde has two competitive dominant reaction pathways. Going with the formation of two side products (INT3 and INT4), simultaneously. The two competitive reactions both consist of two steps: (1) two reactants firstly form a three-membered ring intermediate (INT1) and a twisted four-membered ring intermediate (INT2), respectively, both of which are barrier-free exothermic reactions of 44.5 and 63.0 kJ/mol; (2) then INT1 and INT2 further isomerize to a four-membered ring product (P1) and a chlorine-transfer product (P2) via transitions (TS1 and TS2), respectively, with the barriers of 9.3 and 1.0 kJ/mol; simultaneously, P1 and INT2 react further with acetaldehyde(R2) to give two side products (INT3 and INT4), respectively, which are also barrier-free exothermic reaction of 65.4 and 102.7 kJ/mol.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
M. Benavides-Garcia and K. Balasubramanian, J. Chem. Phys. 97, 7537 (1992).
J. Satge, M. Massol, and P. Riviere, J. Organomet. Chem. 56, 1 (1973).
J. Satge, Pure Appl. Chem. 56, 137 (1984).
D. A. Homer, R. S. Grev, and H. F. Schaefer, J. Am. Chem. Soc. 114, 2093 (1992).
V. Ya. Lee and A. Sekiguchi, Chem. Lett. 33, 84 (2004).
W. A. Herrmann, M. Denk, J. Behm, W. Scherer, F. R. Klingan, H. Bock, M. Solouki, and M. Wagner, Angew. Chem. 104, 1489 (1992).
M. D. Su and S. Y. Chu, Tetrahedron Lett. 40, 4371 (1999).
X. H. Lu, Y. X. Wang, and C. B. Liu, Acta Chim. Sin. 57, 1343 (1999).
X. H. Lu, Y. X. Wang, and C. B. Liu, Chem. J. Chin. Univ. 19, 2001 (1998).
W. H. Harper, E. A. Ferrall, R. K. Hilliard, S. M. Stogner, R. S. Grev, and D. J. Clouthier, J. Am. Chem. Soc. 119, 8361 (1997).
D. A. Hostutler, T. C. Smith, H. Y. Li, and D. J. Clouthier, J. Chem. Phys. 111, 950 (1999).
D. A. Hostutler, D. J. Clouthier, and S. W. Pauls, J. Chem. Phys. 116, 1417 (2002).
S. G. He, B. S. Tackett, and D. J. Clouthier, J. Chem. Phys. 121, 257 (2004).
S. M. Stogner and R. S. Grev, J. Chem. Phys. 108, 5458 (1998).
X. H. Lu, Y. H. Xu, H. B. Yu, and W. R. Wu, J. Phys. Chem. A 109, 6970 (2005).
L. A. Curtis, K. Raghavachari, and J. A. Pople, J. Chem. Phys. 98, 1293 (1993).
K. Fukui, J. Phys. Chem. 74, 4161 (1970).
K. Ishida, K. Morokuma, and A. Komornicki, J. Chem. Phys. 66, 2153 (1981).
Author information
Authors and Affiliations
Corresponding author
Additional information
The article is published in the original.
Rights and permissions
About this article
Cite this article
Lu, X., Han, J., Xu, Y. et al. Theoretical study of the mechanism of cycloaddition reaction between dichloro-germylidene and acetaldehyde. Russ. J. Phys. Chem. 84, 980–986 (2010). https://doi.org/10.1134/S0036024410060166
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0036024410060166