Abstract
The mechanism of the reactions of methane with the gold(III) complexes [AuClx(H2O)4− x ]3−x (x = 2, 3, or 4) was studied by the DFT/PBE method with the SBK basis set. High activation barriers obtained for the reactions of [AuCl4]− and [Au(H2O)Cl3] with methane suggest these reactions cannot proceed under mild conditions. The reaction of the [Au(H2O)2Cl2]+ complex with methane has a rather low energy barrier and proceeds through the formation of an intermediate complex.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
A. E. Shilov, Metal Complexes in Biomimetic Chemical Reactions, CRC Press, Boca Raton—New York, 1997, 302.
A. E. Shilov and G. B. Shul’pin, Coord. Chem. Rev., 1997, 97, 2879.
O. A. Reutov, A. L. Kurts, and K. P. Butin, Organicheskaya khimiya [Organic Chemistry], MGU, Moscow, 1999, 340 pp. (in Russian).
A. E. Shilov and A. A. Shteinman, Coord. Chem. Rev., 1977, 24, 97.
S. S. Stahl, J. A. Labinger, and J. E. Bercaw, J. Am. Chem. Soc., 1995, 117, 9371.
E. M. Siegbahn and R. H. Crabtree, J. Am. Chem. Soc., 1996, 118, 4442.
R. G. Bergman, Science, 1984, 223, 302.
Yu. A. Ustynyuk, L. Yu. Ustynyuk, D. N. Laikov, and V. V. Lunin, Izv. Akad. Nauk, Ser. Khim., 2001, 359 [Russ. Chem. Bull., Int. Ed., 2001, 50, 376].
Y. A. Ustynyuk, L. Y. Ustynyuk, D. N. Laikov, and V. V. Lunin, J. Ogranomet. Chem., 2000, 597, 182.
R. H. Crabtree, Chem. Rev., 1985, 85, 245.
E. G. Chepaikin, A. P. Bezruchenko, A. A. Leshcheva, G. N. Boyko, I. V. Kuzmenkov, E. H. Grigoryan, and A. E. Shilov, J. Mol. Catal. A, 2001, 169, 89.
E. G. Chepaikin, A. P. Bezruchenko, and A. A. Leshcheva, Kinet. Katal., 2002, 43, 550 [Kinet. Catal., 2002, 43 (Engl. Transl.)].
W. R. Mason and H. B. Gray, J. Am. Chem. Soc., 1968, 90, 5721.
M. S. Kharash and H. S. Isbel, J. Am. Chem. Soc., 1931, 53, 3053.
G. B. Shul’pin, J. Organomet. Chem., 1981, 212, 267.
L. A. Levchenko, A. P. Sadkov, N. V. Lariontseva, V. S. Kulikova, A. K. Shilova, and A. E. Shilov, Dokl. Akad. Nauk, 2004, 394, 2 [Dokl. Chem., 2004 (Engl. Transl.)].
G. B. Shul’pin, A. E. Shilov, and E. Suss-Fink, Tetrahedron, 2001, 42, 7253.
J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865.
D. A. Pichugina, A. F. Shestakov, and N. E. Kuz’menko, Zh. Fiz. Khim., 2004, 78, 2027 [Russ. J. Phys. Chem., 2004 (Engl. Transl.)].
D. N. Laikov, Chem. Phys. Lett., 1997, 281, 151.
H. Basch and P. G. Jasien, Can. J. Chem., 1992, 70, 612.
C. Gonzalez and H. B. Schlegel, J. Chem. Phys., 1989, 90, 2154.
H. G. Raubenheimer and S. Cronje, Gold: Progress in Chemistry, Biochemistry, and Technology, Ed. H. Schmidbaur, Wiley, Chichester, 1999, 588.
M. Hargittai, A. Schulz, B. Reffy, and M. Kolonits, J. Am. Chem. Soc., 2001, 123, 1449.
O. Graudejus, S. H. Elder, G. M. Lucier, C. Shen, and N. Bartlett, Inorg. Chem., 1999, 38, 2503.
D. Emsley, The Elements, Clarendon Press, Oxford, 1991.
Author information
Authors and Affiliations
Additional information
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 191–201, February, 2006.
Rights and permissions
About this article
Cite this article
Pichugina, D.A., Shestakov, A.F. & Kuz’menko, N.E. Quantum chemical study of C—H bond activation in methane molecule by AuIII aqua chloride complexes. Russ Chem Bull 55, 195–206 (2006). https://doi.org/10.1007/s11172-006-0237-8
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/s11172-006-0237-8