高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (7): 1475.doi: 10.7503/cjcu20180117
收稿日期:
2018-02-09
出版日期:
2018-07-10
发布日期:
2018-06-14
作者简介:
联系人简介: 王梅艳, 女, 博士, 讲师, 主要从事催化反应微观机理的理论研究. E-mail:基金资助:
FANG Sheng, WANG Meiyan*(), LIU Jingjing, LIU Jingyao
Received:
2018-02-09
Online:
2018-07-10
Published:
2018-06-14
Contact:
WANG Meiyan
E-mail:mywang858@jlu.edu.cn
Supported by:
摘要:
采用密度泛函理论(DFT)方法, 对镍配合物Ni(PPh3)2催化N-烯丙基酰胺异构化生成N-丙烯基酰胺的微观反应机理进行了计算. 反应涉及了C—H键活化、 异构化及还原消除生成新的C—H键等步骤. 对C—H键活化和异构化步骤, 分别考虑了Ni(PPh3)2和Ni(PPh3)的催化活性, 发现均为前者对应的能垒更低; 对异构化步骤, 分别考虑了π-烯丙基和σ-烯丙基机理, 发现前者能垒更低. 在整个反应路径中, 生成产物E异构体的决速能垒为141.8 kJ/mol, 与生成Z异构体的决速能垒(141.1 kJ/mol)仅差0.7 kJ/mol, 与实验上E/Z选择性不高(56/44)一致. Pd(PPh3)2催化的决速中间体和过渡态的计算表明, 生成E和Z异构体的决速能垒较高, 均超过175 kJ/mol, 与实验上Pd(PPh3)4没有催化活性一致. Ni(PPh3)2和Pd(PPh3)2催化活性不同, 可由Ni的d电子对烯丙基阴离子π*反键的反馈作用较Pd更强来解释. 此外, 通过反应物中不同取代基对产物E/Z选择性影响的分析, 发现E/Z选择性不同是由各取代基在生成E和Z异构体的决速过渡态中所受空间位阻不同所导致.
中图分类号:
TrendMD:
方升, 王梅艳, 刘静静, 刘靖尧. 镍配合物催化N-烯丙基酰胺异构化反应机理. 高等学校化学学报, 2018, 39(7): 1475.
FANG Sheng, WANG Meiyan, LIU Jingjing, LIU Jingyao. Reaction Mechanism of Nickel Complex Catalyzed Isomerization of N-Allylamides†. Chem. J. Chinese Universities, 2018, 39(7): 1475.
Fig.1 Energy profiles calculated for C—H bond activation by Ni(PPh3)2(1Ni) to form complex 3Ni^ The calculated free energies relative to 1Ni+N-allyl-4-methylbenzamide are given in kJ/mol.
Fig.2 Energy profiles calculated for isomerization of π-allyl complex 3Ni via the π-allyl mechanism to generate E isomer^ The calculated free energies relative to 1Ni+N-allyl-4-methylbenzamide are given in kJ/mol.
Fig.3 Energy profiles calculated for isomerization of π-allyl complex 3Ni via the σ-allyl mechanism to generate E isomer^ The H atom bonded to Ni is directed outwards(A) and inwards(B). The calculated free energies relative to 1Ni+N-allyl-4-methylbenzamide are given in kJ/mol.
Fig.4 Energy profiles calculated for isomerization of π-allyl complex 3'Ni via the π-allyl(A) and σ-allyl(B) mechanism^ The calculated free energies relative to 1Ni+N-allyl-4-methylbenzamide are given in kJ/mol.
Fig.5 Structures and energies of the rate-determining intermediate 2ZNi and five lowest transition states on the energy profiles to generate Z isomer^The calculated free energies relative to 1Ni+N-allyl-4-methylbenzamide are given in kJ/mol.
Fig.6 Structures and energies of the rate-determining intermediate 2Pd and transition states TS34aPd and TS34ZaPd on the energy profiles to generate E and Z isomer^The calculated free energies relative to 1Pd+N-allyl-4-methylbenzamide are given in kJ/mol.
Fig.7 Energy decomposition analyses of the energy barriers(kJ/mol) from rate-determining intermediates 2M to transition states TS34aM^ a. The energy of Ni; b. the energy of Pd; c. the energy difference of Ni and Pd.
Fig.8 Structures and energies(kJ/mol) of two rate-determining transition states TS34a-tBu and TS34Za-tBu(A) for reactant with R=tBu (relative to 1Ni+N-allyl-pivaloylamide), as well as TS34a and TS34Za(B) for reactant with R=p-MeC6H4 (relative to 1Ni+N-allyl-4-methylbenzamide)
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