张志平, 王晨, 傅尧, 郭庆祥. Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method[J]. Chinese Journal of Chemical Physics , 2010, 23(6): 669-674. doi: 10.1088/1674-0068/23/06/669-674
Citation: 张志平, 王晨, 傅尧, 郭庆祥. Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method[J]. Chinese Journal of Chemical Physics , 2010, 23(6): 669-674. doi: 10.1088/1674-0068/23/06/669-674

Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method

doi: 10.1088/1674-0068/23/06/669-674
Funds:  This work was supported by the National Natural Sci-ence Foundation of China (No.20972148) and the Pro-gram for New Century Excellent Talents in University (No.080519).
  • Received Date: 2010-07-21
  • The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods (B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method) were exam-ined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM(CCSD(T)/6-311++G(2df,2p):B3LYP/6-311++G(2df,2p))// B3LYP/6-31G(d)/PCM/UFF) method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.
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Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method

doi: 10.1088/1674-0068/23/06/669-674
Funds:  This work was supported by the National Natural Sci-ence Foundation of China (No.20972148) and the Pro-gram for New Century Excellent Talents in University (No.080519).

Abstract: The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods (B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method) were exam-ined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM(CCSD(T)/6-311++G(2df,2p):B3LYP/6-311++G(2df,2p))// B3LYP/6-31G(d)/PCM/UFF) method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.

张志平, 王晨, 傅尧, 郭庆祥. Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method[J]. Chinese Journal of Chemical Physics , 2010, 23(6): 669-674. doi: 10.1088/1674-0068/23/06/669-674
Citation: 张志平, 王晨, 傅尧, 郭庆祥. Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method[J]. Chinese Journal of Chemical Physics , 2010, 23(6): 669-674. doi: 10.1088/1674-0068/23/06/669-674

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