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Volumn 26, Issue 10, 2007, Pages 2589-2597

Facile intermolecular aryl-F bond cleavage in the presence of aryl C-H bonds: Is the η2-arene intermediate bypassed?

Author keywords

[No Author keywords available]

Indexed keywords

ARYL; C-H BONDS; FACILE INTERMOLECULAR; PHENYLDIMETHYLSILANE;

EID: 34249034897     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om070099j     Document Type: Article
Times cited : (40)

References (68)
  • 29
    • 34249061489 scopus 로고    scopus 로고
    • 31P NMR spectrum closely matched that observed in a H NMR spectrum for an authentic mixture of 2 and 3.
    • 31P NMR spectrum closely matched that observed in a H NMR spectrum for an authentic mixture of 2 and 3.
  • 30
    • 34249036792 scopus 로고    scopus 로고
    • By this reasoning, two atropisomers are expected and only two isomers are experimentally observed
    • By this reasoning, two atropisomers are expected and only two isomers are experimentally observed.
  • 31
    • 34249001066 scopus 로고    scopus 로고
    • p.a is not a good reflection of the formal reduction potential, E°, because of an exceptionally fast chemical reaction (substitution) following the electrochemical event (EC) mechanism. This would shift the anodic peak negative.
    • p.a is not a good reflection of the formal reduction potential, E°, because of an exceptionally fast chemical reaction (substitution) following the electrochemical event (EC) mechanism. This would shift the anodic peak negative.
  • 38
    • 34249043914 scopus 로고    scopus 로고
    • 6A and 6B are almost certainly in equilibrium, based on our previous examination of intraannular and interannular isomerization rates for naphthalenes.
    • 6A and 6B are almost certainly in equilibrium, based on our previous examination of intraannular and interannular isomerization rates for naphthalenes.
  • 40
    • 34249089602 scopus 로고    scopus 로고
    • Originally this is formed as the kinetic isomer in which O is oriented away from the phosphine. Over time this rearranges to the thermodynamic isomer in which the oxygen is oriented toward the phosphine
    • Originally this is formed as the kinetic isomer in which O is oriented away from the phosphine. Over time this rearranges to the thermodynamic isomer in which the oxygen is oriented toward the phosphine.
  • 41
    • 34248998506 scopus 로고    scopus 로고
    • A second, small coupling constant is also present of J = 5.9 Hz.
    • A second, small coupling constant is also present of J = 5.9 Hz.
  • 42
    • 34248996611 scopus 로고    scopus 로고
    • Gaussian, Inc, Wallingford, CT
    • Frisch, M. J., et al. Gaussian 03, Revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
    • (2004) Gaussian 03, Revision , Issue.C.02
    • Frisch, M.J.1
  • 49
    • 34249090266 scopus 로고    scopus 로고
    • The half-life for benzene substitution at 22°C is largely unaffected by either the nature or the concentration of the incoming ligand.
    • The half-life for benzene substitution at 22°C is largely unaffected by either the nature or the concentration of the incoming ligand.
  • 52
    • 34249045143 scopus 로고    scopus 로고
    • The approach of fluorobenzene to the agent [W] was traced for two pathways, with the reaction coordinate being the W-F or W-H distance, respectively. The first pathway led to a well-defined equilibrium complex A and a transition state B° from which the CF activated product derives. The second pathway led smoothly to the CH activation product. Since pure density functionals are known to underestimate activation barriers (see Stanton, R. V, Merz, Jr, K. M. J. Chem. Phys. 1994, 100, 434) and LSDA in particular overestimates binding energy in stable molecules, and because an admixture of HF exchange into the density functional, such as is done in the B3LYP formulation, improves estimates of barrier heights relative to those obtained by pure DFT functionals, we retraced the path with B3LYP/LANL2DZ model chemistry calculations. This produced a shallow minimum with an activation barrier no greater than 1 kcal/mol. We reoptimized the structure of the wea
    • The approach of fluorobenzene to the agent [W] was traced for two pathways, with the reaction coordinate being the W-F or W-H distance, respectively. The first pathway led to a well-defined equilibrium complex A and a transition state B° from which the CF activated product derives. The second pathway led smoothly to the CH activation product. Since pure density functionals are known to underestimate activation barriers (see Stanton, R. V.; Merz, Jr, K. M. J. Chem. Phys. 1994, 100, 434) and LSDA in particular overestimates binding energy in stable molecules, and because an admixture of HF exchange into the density functional, such as is done in the B3LYP formulation, improves estimates of barrier heights relative to those obtained by pure DFT functionals, we retraced the path with B3LYP/LANL2DZ model chemistry calculations. This produced a shallow minimum with an activation barrier no greater than 1 kcal/mol. We reoptimized the structure of the weak complex, constraining the C-H and H-W distances and the C-H-W angle to the values obtained in B3LYP/ LANL2DZ. The energies quoted in the text for the CH complex and the transition state on the path toward the CH activated structure are LSDA/ LANL2DZ values obtained at these constrained structures. We are confident in the values of the energies of these points along the CH activation path within 5 kcal/mol or less and consider that the values quoted are upper bounds to the values at corresponding points on the fully optimized path.
  • 53
    • 0042914692 scopus 로고    scopus 로고
    • For more on the use of LSDA in organometallic structures see:, ACS: Washington, DC
    • For more on the use of LSDA in organometallic structures see: Salahub, D. R.; Chretien, S.; Milet, A; Proynov E. I. In ACS Symp. Ser. 721; ACS: Washington, DC, 1999.
    • (1999) ACS Symp. Ser , vol.721
    • Salahub, D.R.1    Chretien, S.2    Milet, A.3    Proynov, E.I.4
  • 54
    • 34249109764 scopus 로고    scopus 로고
    • Koch, W.; Holthausen, M. C. In A Chemist's Guide to Density Functional Theory, 2nd ed.; Truhlar, D. G., Morokuma K., Eds.; Wiley-VCH: Weinheim, Germany 2001.
    • Koch, W.; Holthausen, M. C. In A Chemist's Guide to Density Functional Theory, 2nd ed.; Truhlar, D. G., Morokuma K., Eds.; Wiley-VCH: Weinheim, Germany 2001.
  • 60
    • 0042498395 scopus 로고
    • Marcinicec, B, Chojnowski, J, Eds, Gordon and Breach: Yverdon-lesBains, Switzerland
    • Schubert, U. In Advances in Organosilicon Chemistry; Marcinicec, B., Chojnowski, J., Eds.; Gordon and Breach: Yverdon-lesBains, Switzerland, 1994.
    • (1994) Advances in Organosilicon Chemistry
    • Schubert, U.1
  • 61
    • 0942281376 scopus 로고
    • Marciniec, B, Chojonwski, J, Eds, Gordon and Breach: Switzerland
    • Schubert, U. In Progress in Organosilicon Chemistry; Marciniec, B., Chojonwski, J., Eds.; Gordon and Breach: Switzerland, 1995; p 287.
    • (1995) Progress in Organosilicon Chemistry , pp. 287
    • Schubert, U.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.