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Volumn 129, Issue 17, 2007, Pages 5492-5502

On the theory of organic catalysis "on water"

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOLS; DEUTERIUM; EMULSIONS; HYDROGEN BONDS; ISOTOPES; MOLECULAR STRUCTURE;

EID: 34247897075     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja068120f     Document Type: Article
Times cited : (609)

References (88)
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  • 9
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    • Structure and Reactivity in Aqueous Solution
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    • (1994) ACS Symposium Series , vol.568
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    • Li, C. J. Chem. Rev. 1993, 93, 2023-2035.
    • (1993) Chem. Rev , vol.93 , pp. 2023-2035
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  • 43
    • 34247896136 scopus 로고    scopus 로고
    • Considering the liquidlike disordered film structure of the surface of ice, this prescribed density should be interpreted as a statistical estimate
    • Considering the liquidlike disordered film structure of the surface of ice, this prescribed density should be interpreted as a statistical estimate.
  • 46
    • 34247876620 scopus 로고    scopus 로고
    • We assume for the surface reaction that DMAD is always multiply H bonded to water since the free OH bonds are always available at the interface with almost zero cost. The stabilizing energy of DMAD at the water interface as a result of H bond formation with three water molecules is estimated to be -4.4 kcal/mol at B3LYP/6-31G*
    • We assume for the surface reaction that DMAD is always multiply H bonded to water since the free OH bonds are always available at the interface with almost zero cost. The stabilizing energy of DMAD at the water interface as a result of H bond formation with three water molecules is estimated to be -4.4 kcal/mol at B3LYP/6-31G*.
  • 50
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    • If emulsifiers such as surfactants are used, smaller droplets can be obtained with a radius of ∼0.1 μm. Without emulsifiers, the size of n-alkane droplets, n = 6-16, is on the order of micrometers.
    • If emulsifiers such as surfactants are used, smaller droplets can be obtained with a radius of ∼0.1 μm. Without emulsifiers, the size of n-alkane droplets, n = 6-16, is on the order of micrometers.
  • 53
    • 34247888107 scopus 로고    scopus 로고
    • - using 6-311++G** at TS1.
    • - using 6-311++G** at TS1.
  • 60
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    • Chandler, D. Nature 2005, 437, 640-647.
    • (2005) Nature , vol.437 , pp. 640-647
    • Chandler, D.1
  • 62
    • 34247888106 scopus 로고    scopus 로고
    • The H bond energy between water and DMAD was estimated using the optimized geometry of DMAD + three water molecules, denoted by 2w in Figure 3. The interaction energy of DMAD with each water molecule in 2w was then computed by removing the other two water molecules. This approach yielded DMAD-water interactions energies of 2-4 kcal/mol, variation depending on the local interacting groups, carbonyl oxygens or nitrogens.
    • The H bond energy between water and DMAD was estimated using the optimized geometry of DMAD + three water molecules, denoted by 2w in Figure 3. The interaction energy of DMAD with each water molecule in 2w was then computed by removing the other two water molecules. This approach yielded DMAD-water interactions energies of 2-4 kcal/mol, variation depending on the local interacting groups, carbonyl oxygens or nitrogens.
  • 65
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    • While the homogeneous reaction medium in the cited experiments was the mixture of methanol and water, it has been also shown that the local tetrahedral coordination of water is still roughly retained in a methanol/water mixture, as in pure water. See ref 65
    • While the homogeneous reaction medium in the cited experiments was the mixture of methanol and water, it has been also shown that the local tetrahedral coordination of water is still roughly retained in a methanol/water mixture, as in pure water. See ref 65.
  • 67
    • 34247896135 scopus 로고    scopus 로고
    • We assume for simplicity that water molecules, instead of methanol molecules, form H-bonds with DMAD preferably in a methanol/water mixture. For water, the other OH group of water that is not H-bonded to the reactant can still form H bonds with bulk water acting as an anchor, while for methanol, that anchoring is difficult because of the methyl end
    • We assume for simplicity that water molecules, instead of methanol molecules, form H-bonds with DMAD preferably in a methanol/water mixture. For water, the other OH group of water that is not H-bonded to the reactant can still form H bonds with bulk water acting as an anchor, while for methanol, that anchoring is difficult because of the methyl end.
  • 68
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    • Since there might be more H-bonds involved in the homogeneous reaction than in the surface reaction, the energetic consequence might also be different. However, to a rough approximation, we assume that the relative H-bond stabilization of the TS compared to the reactants as a result of H-bond formation for the homogeneous reaction is roughly the same as that for the surface reaction, namely about 7 kcal/mol in favor of the TS
    • Since there might be more H-bonds involved in the homogeneous reaction than in the surface reaction, the energetic consequence might also be different. However, to a rough approximation, we assume that the relative H-bond stabilization of the TS compared to the reactants as a result of H-bond formation for the homogeneous reaction is roughly the same as that for the surface reaction, namely about 7 kcal/mol in favor of the TS.
  • 72
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    • D = 1.2. These unpublished experimental data were kindly provided by Drs. Narayan and Sharpless from a private communication.
    • D = 1.2. These unpublished experimental data were kindly provided by Drs. Narayan and Sharpless from a private communication.
  • 73
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    • 2O are 0.912 and 1.121 mPa·s, respectively, at room temperature. Reichardt, C. Solvents and Solvent Effects in Organic Chemistry, 3rd ed.; Wiley: Weinheim, Germany, 2003.
    • 2O are 0.912 and 1.121 mPa·s, respectively, at room temperature. Reichardt, C. Solvents and Solvent Effects in Organic Chemistry, 3rd ed.; Wiley: Weinheim, Germany, 2003.
  • 74
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    • 2O by the International Association for the Properties of Water and Steam (IAPWS) are 71.98 ± 0.36 and 71.87 ± 0.50. respectively (1997).
    • 2O by the International Association for the Properties of Water and Steam (IAPWS) are 71.98 ± 0.36 and 71.87 ± 0.50. respectively (1997).
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    • Transition states in organic chemistry: Ab initio
    • Schleyer, P. V. R, Ed, Wiley: Chichester
    • Wiest, O. Transition states in organic chemistry: Ab initio. In Encyclopedia of Computational Chemistry; Schleyer, P. V. R., Ed.; Wiley: Chichester, 1998; pp 3104-3114.
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    • For the neat reaction, we were unable to locate the concerted transition state that may be expected from the symmetry consideration as described in the main text, despite the extensive search for it. Stationary points located close to the concerted configuration turned out to be a second-order saddle point
    • For the neat reaction, we were unable to locate the concerted transition state that may be expected from the symmetry consideration as described in the main text, despite the extensive search for it. Stationary points located close to the concerted configuration turned out to be a second-order saddle point.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.