메뉴 건너뛰기




Volumn 26, Issue 25, 2007, Pages 6213-6218

On the intermediacy of chlorinated alkylcobalt complexes in the reductive dehalogenation of chloroalkenes. A first-principles molecular dynamics study

Author keywords

[No Author keywords available]

Indexed keywords

CHLORINATION; DEHALOGENATION; FREE ENERGY; MOLECULAR DYNAMICS; OLEFINS; VITAMINS;

EID: 37249073408     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om7007474     Document Type: Article
Times cited : (11)

References (61)
  • 2
    • 21844449665 scopus 로고    scopus 로고
    • Brown, K. L. Chem. Rev. 2005, 105, 2075-2149.
    • (2005) Chem. Rev , vol.105 , pp. 2075-2149
    • Brown, K.L.1
  • 10
    • 17144404151 scopus 로고    scopus 로고
    • For analogous dechlorination of alkyl halides, see, for example: a, and references cited therein
    • For analogous dechlorination of alkyl halides, see, for example: (a) Argüello, J. E.; Costentin, C.; Griveau, S.; Saveant, J.-M. J. Am. Chem. Soc. 2005, 127, 5049-5055 and references cited therein.
    • (2005) J. Am. Chem. Soc , vol.127 , pp. 5049-5055
    • Argüello, J.E.1    Costentin, C.2    Griveau, S.3    Saveant, J.-M.4
  • 11
    • 34249297954 scopus 로고    scopus 로고
    • For a recent report on dechlorination of DDT, see: b
    • For a recent report on dechlorination of DDT, see: (b) Jabbar, M. A.; Shimakoshi, H.; Hisaeda, Y. Chem. Commun. 2007, 1653-1655.
    • (2007) Chem. Commun , pp. 1653-1655
    • Jabbar, M.A.1    Shimakoshi, H.2    Hisaeda, Y.3
  • 20
  • 21
    • 0034662844 scopus 로고    scopus 로고
    • Histidine
    • (b) Sprik, M. Chem. Phys. 2000, 258, 139-150. Histidine:
    • (2000) Chem. Phys , vol.258 , pp. 139-150
    • Sprik, M.1
  • 27
    • 37249013692 scopus 로고    scopus 로고
    • CPMD Version 3.7.0; copyright by IBM Corp. and Max-Planck-Institut für Festkörperforschung, Stuttgart, Germany
    • CPMD Version 3.7.0; copyright by IBM Corp. and Max-Planck-Institut für Festkörperforschung, Stuttgart, Germany.
  • 34
    • 22944439420 scopus 로고    scopus 로고
    • See: VandeVondele, J.; Mohamed, F.; Krack, M.; Hutter, J.; Sprik, M.; Parrinello, M. J. Chem. Phys. 2005, 122, 014515 and references cited therein.
    • See: VandeVondele, J.; Mohamed, F.; Krack, M.; Hutter, J.; Sprik, M.; Parrinello, M. J. Chem. Phys. 2005, 122, 014515 and references cited therein.
  • 35
    • 0001702831 scopus 로고    scopus 로고
    • See, for instance:, and references cited therein
    • See, for instance: Sprik, M.; Ciccotti, G. J. Chem. Phys. 1998, 109, 7737 and references cited therein.
    • (1998) J. Chem. Phys , vol.109 , pp. 7737
    • Sprik, M.1    Ciccotti, G.2
  • 36
    • 37249047791 scopus 로고    scopus 로고
    • -1 for the derived energies. Each new point was started from the final, equilibrated configuration of the previous one. See Supporting Information for plots of the 〈f(ξ)〉 values.
    • -1 for the derived energies. Each new point was started from the final, equilibrated configuration of the previous one. See Supporting Information for plots of the 〈f(ξ)〉 values.
  • 37
    • 37249000188 scopus 로고    scopus 로고
    • NVT simulations yield ΔA; because the actual change at constant pressure is very small, ΔA and ΔG should be very similar
    • NVT simulations yield ΔA; because the actual volume change at constant pressure is very small, ΔA and ΔG should be very similar.
  • 39
    • 10144223417 scopus 로고
    • (b) Hay, P. J. J. Chem. Phys. 1977, 66, 4377-4384.
    • (1977) J. Chem. Phys , vol.66 , pp. 4377-4384
    • Hay, P.J.1
  • 42
    • 37249073216 scopus 로고    scopus 로고
    • Generated automatically according to the procedure implemented in Gaussian 03.
    • Generated automatically according to the procedure implemented in Gaussian 03.
  • 44
    • 0001652762 scopus 로고    scopus 로고
    • In particular, as far as geometries of transition metal complexes are concerned, the popular B3LYP functional need not be superior to pure, gradient-corrected variants such as BP86, see, for instance: (a) Hamprecht, F. A. H.; Cohen, A. J.; Tozer, D. J.; Handy, N. C. J. Chem. Phys. 1998, 109, 6264-6271.
    • In particular, as far as geometries of transition metal complexes are concerned, the popular B3LYP functional need not be superior to pure, gradient-corrected variants such as BP86, see, for instance: (a) Hamprecht, F. A. H.; Cohen, A. J.; Tozer, D. J.; Handy, N. C. J. Chem. Phys. 1998, 109, 6264-6271.
  • 49
    • 84962428785 scopus 로고    scopus 로고
    • As implemented in Gaussian 03: (a) Barone, V.; Cossi, M.; Tomasi, J. J. Comput. Chem. 1998, 19, 404-417.
    • As implemented in Gaussian 03: (a) Barone, V.; Cossi, M.; Tomasi, J. J. Comput. Chem. 1998, 19, 404-417.
  • 52
    • 37249025499 scopus 로고    scopus 로고
    • Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Montgomery, J. A, Jr, Vreven, 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, H. P, Cross, J. B, Bakken, V, 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, Salvafdor, 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, Kei
    • Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, 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, H. P.; Cross, J. B.; Bakken, V.; 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.; Salvafdor, 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. Gaussian 03; Gaussian, Inc.: Wallingford, CT, 2004.
  • 55
    • 37249007561 scopus 로고    scopus 로고
    • 2 in eq 5 would increase.
    • 2 in eq 5 would increase.
  • 56
    • 37249033000 scopus 로고    scopus 로고
    • -13.9 kcal/mol in single-point PCM energy computations employing the RI-BP86/AE1-optimized geometries, AE2 basis, and the B3LYP hybrid functional. The binding energy of water thus appears to be not very sensitive to the functional employed.
    • -13.9 kcal/mol in single-point PCM energy computations employing the RI-BP86/AE1-optimized geometries, AE2 basis, and the B3LYP hybrid functional. The binding energy of water thus appears to be not very sensitive to the functional employed.
  • 57
    • 37249015764 scopus 로고    scopus 로고
    • + ion (which, in the gas-phase-optimized structures, formed two OH⋯ Cl interactions with the Cl atoms on the a-carbon), and the two Co - C bonds were constrained to 2.1 and 3.2 Å (mean values from constrained CPMD simulations at the last point in Figure 4), to prevent any formation, full or partial, of metallacycle 2 upon removal of the water in trans position.
    • + ion (which, in the gas-phase-optimized structures, formed two OH⋯ Cl interactions with the Cl atoms on the a-carbon), and the two Co - C bonds were constrained to 2.1 and 3.2 Å (mean values from constrained CPMD simulations at the last point in Figure 4), to prevent any formation, full or partial, of metallacycle 2 upon removal of the water in trans position.
  • 58
    • 84890021933 scopus 로고    scopus 로고
    • In addition, a significant fraction of these binding energies, ca. 4 kcal/mol, is indicated to arise from basis-set superposition error according to Counterpoise calculations, cf, Boys, S. F, Bernardi, F. Mol. Phys. 1970, 79, 553-566, which further underscores the lability of the water ligands. It should be noted that the CPMD simulations with their periodic, plane-wave basis set do not suffer from this error
    • In addition, a significant fraction of these binding energies, ca. 4 kcal/mol, is indicated to arise from basis-set superposition error (according to Counterpoise calculations, cf., Boys, S. F.; Bernardi, F. Mol. Phys. 1970, 79, 553-566), which further underscores the lability of the water ligands. It should be noted that the CPMD simulations with their periodic, plane-wave basis set do not suffer from this error.
  • 61
    • 0038937322 scopus 로고    scopus 로고
    • Base-off intermediates are frequently invoked for reactive intermediates believed to be central to the chemistry of the cofactor, see, for example: Lexa, D, Saveant, J.-M. Acc. Chem. Res. 1983, 16, 235-243
    • Base-off intermediates are frequently invoked for reactive intermediates believed to be central to the chemistry of the cofactor, see, for example: Lexa, D.; Saveant, J.-M. Acc. Chem. Res. 1983, 16, 235-243.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.