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Volumn 27, Issue 7, 2008, Pages 1384-1392

Theoretical studies of the sp2 versus sp3 C-H bond activation chemistry of 2-picoline by (C5Me5) 2An(CH3)2 complexes (An = Th, U)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; CHEMICAL BONDS; DENSITY FUNCTIONAL THEORY; ISOMERS; METAL COMPLEXES;

EID: 84962433687     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om700927n     Document Type: Article
Times cited : (36)

References (55)
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    • This field in transition metal has been extensively reviewed. For example: (a) Davies, J. A. W. P. L, Liebman, J. F, Greenberg, A, Eds. Selective Hydrogencarbon Activation: Principles and Progress; VCH Publishers: New York, 1990
    • This field in transition metal has been extensively reviewed. For example: (a) Davies, J. A. W. P. L.; Liebman, J. F.; Greenberg, A., Eds. Selective Hydrogencarbon Activation: Principles and Progress; VCH Publishers: New York, 1990.
  • 11
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    • Activation and Functionalization of C-H Bonds
    • Goldberg, K. I, Goldman, A. S, Eds, American Chemical Society: Washington, DC, In
    • (f) Goldberg, K. I.; Goldman, A. S., Eds. Activation and Functionalization of C-H Bonds; ACS Symp. Ser. No. 885; American Chemical Society: Washington, DC, 2004, In.
    • (2004) ACS Symp. Ser , vol.885
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    • Theoretical Studies of the Electronic Structure of Compounds of the Actinide Elements
    • 3rd ed, Morss, L. R, Edelstein, N. M, Fuger, J, Eds, Springer: Dordrecht, The Netherlands
    • Kaltsoyannis N.; Hay, P. J.; Li, J ; Blaudeau, J. P.; Bursten, B. E. Theoretical Studies of the Electronic Structure of Compounds of the Actinide Elements. In The Chemistry of the Actinide and Tranactinide Elements, 3rd ed.; Morss, L. R., Edelstein, N. M., Fuger, J., Eds.; Springer: Dordrecht, The Netherlands, 2006; Vol. 3.
    • (2006) The Chemistry of the Actinide and Tranactinide Elements , vol.3
    • Kaltsoyannis, N.1    Hay, P.J.2    Li, J.3    Blaudeau, J.P.4    Bursten, B.E.5
  • 28
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    • 2): -0.54 kcal/mol for B3LYP, -0.71 kcal/mol for B3PW91, -1.42 kcal/mol for TPSS, and -1.92 kcal/mol for BMK. The chosen functional B3LYP described the essential properties and fundamental chemistry of these compounds but slightly underestimated the energy difference compared to others.
    • 2): -0.54 kcal/mol for B3LYP, -0.71 kcal/mol for B3PW91, -1.42 kcal/mol for TPSS, and -1.92 kcal/mol for BMK. The chosen functional B3LYP described the essential properties and fundamental chemistry of these compounds but slightly underestimated the energy difference compared to others.
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    • Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Montgomery, J. A, Vreven, J. 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, J. P, Cross, J. B, 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-Laha
    • Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A.; Vreven, J. 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, J. P.; Cross, J. B.; 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.; Pople, J. A. Gaussian03, Revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
  • 55
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    • We have used electronic energies here to examine the reaction pathways. The quantitative results and the trends between Th and U would have been equally well given by the enthalpies at 298 K (see Tables S5 and S6 in the Supporting Information, The Gibbs free energies at 298 K also give consistent predictions as given above with the exception of the relative ordering of the Th sp 2 and sp3 activation barriers, 1.4 kcal/mol) compared to ZPE corrected energies, 0.7 kcal/mol) The quantities in context use electronic energies without zero-point corrections. Because the low rotation mode of the methyl group on the picoline ring is constrained in the sp3 activation path, the frequencies of TS5A-2A(sp3) are higher than that of TS5A-1A(sp2, As a result, the lower entropy contribution of TS5A-2A(sp3) leads to a higher Gibbs free energy (G, H, TS) compared to TS5A-1ASP
    • 2). This observation also holds for the uranium system as well. However, the entropy contributions are calculated for gas-phase species. For reactions in solution, as in the present calculations, the translational, rotational, and low-frequency vibrational contributions to the entropy can be reduced. And as a result, the gas-phase free energies may overestimate the reaction barrier. For a recent discussion, see ref 38.


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