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Volumn 26, Issue 20, 2007, Pages 4896-4903

Steric and electronic effects in linkage isomerization reactions of M(CO)5(L) (M = Cr, Mo, W; L = 2-methyl-2,3-dihydrofuran, 2,3-dihydropyran)

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION SPECTROSCOPY; CYCLOHEXANE; FURAN RESINS; INFRARED ABSORPTION; ISOMERIZATION; PHOTOLYSIS; REACTION KINETICS;

EID: 34948826555     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om700456x     Document Type: Article
Times cited : (7)

References (69)
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    • (b) Werner, A. Ber. 1907, 40, 765.
    • (1907) Ber , vol.40 , pp. 765
    • Werner, A.1
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    • Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Zakrzewski, V. G, Montgomery, J. A, Stratmann, R. E, Burant, J. C, Dapprich, S, Milam, J. M, Daniels, A. D, Kudin, K. N, Strain, M. C, Farkas, O, Tomasi, J, Barone, V, Cossi, M, Cammi, R, Mennucci, B, Pomelli, C, Adamo, C, Clifford, S, Ochterski, J, Petersson, G. A, Ayala, P. Y, Cui, Q, Morokuma, K, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Cioslowski, J, Ortiz, J. V, Stefanov, B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Gomperts, R, Martin, R. L, Fox, D. J, Keith, T, Al-Laham, M. A, Peng, C. Y, Nanayakkara, A, Gonzalez, C, Challacombe, M, Gill, P. M. W, Johnson, B. G, Chen, W, Wong, M. W, Andres, J. L, Head-Gordon, M, Replogle, E. S, Pople, J. A. Gaussian 98 Revision A.7, Gaussian, Inc, Pittsburgh, 1998
    • Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Milam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98 (Revision A.7); Gaussian, Inc.: Pittsburgh, 1998.
  • 49
    • 34948833315 scopus 로고    scopus 로고
    • The LANL2DZ basis set for W was obtained from the Extensible Computational Chemistry Environment Basis Set Database, Version 02/02/06, as developed and distributed by the Molecular Science Computing Facility, Environmental and Molecular Sciences Laboratory, which is part of the Pacific Northwest Laboratory, P.O. Box 999, Richland, WA 99352, and funded by the U.S. Department of Energy.
    • (b) The LANL2DZ basis set for W was obtained from the Extensible Computational Chemistry Environment Basis Set Database, Version 02/02/06, as developed and distributed by the Molecular Science Computing Facility, Environmental and Molecular Sciences Laboratory, which is part of the Pacific Northwest Laboratory, P.O. Box 999, Richland, WA 99352, and funded by the U.S. Department of Energy.
  • 50
    • 34948829253 scopus 로고    scopus 로고
    • eq.
    • eq.
  • 52
    • 34948890664 scopus 로고    scopus 로고
    • obs, which depends only on dΔA/dt, remains independent of [L] even in the presence of a nonzero baseline.
    • obs, which depends only on dΔA/dt, remains independent of [L] even in the presence of a nonzero baseline.
  • 53
    • 34948893583 scopus 로고    scopus 로고
    • We thank one of the reviewers of the manuscript for bringing this point to our attention.
    • We thank one of the reviewers of the manuscript for bringing this point to our attention.
  • 66
    • 34948837467 scopus 로고    scopus 로고
    • 5(2,5-DHF) was sufficiently high that we were able to place only a lower limit on its value and, hence, were not able to calculate ΔH° and ΔS° for the equilibrium.
    • 5(2,5-DHF) was sufficiently high that we were able to place only a lower limit on its value and, hence, were not able to calculate ΔH° and ΔS° for the equilibrium.
  • 69
    • 34948841623 scopus 로고    scopus 로고
    • While the DFT calculations appear to give fairly reliable structural information, they are not sufficiently accurate to give unambiguous energetic information about the various M(CO)5(L) complexes. As shown in Table 4, the uncertainties in the calculated energetics of different systems are of similar magnitude to the differences between them, and in some cases, changing the basis set or functional can change the predicted value of ΔG° from negative to positive
    • 5(L) complexes. As shown in Table 4, the uncertainties in the calculated energetics of different systems are of similar magnitude to the differences between them, and in some cases, changing the basis set or functional can change the predicted value of ΔG° from negative to positive.


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