高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (10): 1954.doi: 10.7503/cjcu20150326
收稿日期:
2015-04-22
出版日期:
2015-10-10
发布日期:
2015-09-14
作者简介:
联系人简介: 方德彩, 男, 教授, 博士生导师, 主要从事计算化学研究. E-mail:基金资助:
Received:
2015-04-22
Online:
2015-10-10
Published:
2015-09-14
Contact:
FANG Decai
E-mail:dcfang@bnu.edu.cn
Supported by:
摘要:
采用多种密度泛函理论方法(如CAM-B3LYP, M062x和wB97x方法), 并辅以极化连续介质模型对叔丁氧基自由基(tBuO·)与一系列胺类、 烷烃、 醇类和醚类反应物之间氢迁移反应的反应机理进行研究. 计算结果表明, 这类氢迁移反应主要受熵的控制. 通过对液相平动熵和气相平动熵得到的活化自由能数据进行对比, 可以看出, 使用气相平动熵得出的活化自由能明显偏高于实验测量值, 而以液相平动熵计算的反应活化自由能垒与实际结果相近, 3种方法对胺类和烷烃类反应物体系得出的结果更可靠, 对醇类和醚类反应物体系自由能垒则略低.
中图分类号:
TrendMD:
李悦, 方德彩. 叔丁氧基自由基引发氢迁移过程的理论研究. 高等学校化学学报, 2015, 36(10): 1954.
LI Yue, FANG Decai. Density Functional Theory Studies on the t-Butoxyl Radical Mediated Hydrogen Atom Transfer Reactions†. Chem. J. Chinese Universities, 2015, 36(10): 1954.
Fig.1 Main geometric parameters(nm) of 21 transition states in benzene solution, obtained with CAM-B3LYP, M062x and wB97x from top to bottom, respectively2a—2h: Amines; 2i—2o: hydrocarbons; 2p—2q: alcohols; 2r—2u: ethers.
Fig.2 Calculated activation entropies(ΔS≠) for 21 hydrogen abstractions(1+2a—2u) obtained with gas-phase translational entropies ΔS≠(gas) for those methods and with solution translational entropies ΔS≠(sol) for those methods with PCM(in THF), along with experimental measurements[18]
Species | Reaction | CAM-B3LYPa | CAM-B3LYPb | M062xa | wB97xa | Expt.c | ||||
---|---|---|---|---|---|---|---|---|---|---|
ΔG≠(g)d/ (kJ·mol-1) | ΔG≠(l)e/ (kJ·mol-1) | ΔG≠(g) / (kJ·mol-1) | ΔG≠(l)/ (kJ·mol-1) | ΔG≠(g)/ (kJ·mol-1) | ΔG≠(l)/ (kJ·mol-1) | ΔG≠(g)/ (kJ·mol-1) | ΔG≠(l)/ (kJ·mol-1) | |||
Amines | 1+2a | 51.0 | 23.0 | 57.3 | 28.4 | 43.1 | 15.1 | 48.5 | 20.5 | 29.7 |
1+2b | 54.4 | 26.3 | 61.1 | 31.8 | 48.1 | 19.7 | 53.9 | 25.5 | 31.4 | |
1+2c | 64.0 | 35.1 | 63.6 | 35.1 | 56.5 | 28.0 | 65.7 | 37.2 | 32.6 | |
1+2d | 55.6 | 27.6 | 66.9 | 38.5 | 53.1 | 24.7 | 54.4 | 26.8 | 27.6 | |
1+2e | 45.6 | 18.4 | 51.4 | 23.8 | 43.5 | 16.3 | 47.3 | 20.5 | 27.6 | |
1+2f | 65.7 | 36.8 | 65.6 | 36.4 | 57.7 | 28.9 | 64.4 | 36.4 | 33.0 | |
1+2g | 70.7 | 43.1 | 68.6 | 40.6 | 63.6 | 36.8 | 72.8 | 45.6 | 33.9 | |
1+2h | 51.4 | 24.3 | 53.1 | 24.7 | 48.5 | 20.1 | 53.9 | 27.2 | 27.2 | |
Hydrocarbons | 1+2i | 67.7 | 38.9 | 76.1 | 47.7 | 54.8 | 26.3 | 64.4 | 35.5 | 36.8 |
1+2j | 66.5 | 37.6 | 69.0 | 39.7 | 59.0 | 30.1 | 68.2 | 38.9 | 35.5 | |
1+2k | 63.6 | 34.7 | 63.1 | 33.9 | 57.7 | 29.3 | 65.2 | 36.8 | 36.0 | |
1+2l | 70.3 | 40.6 | 68.6 | 39.3 | 63.6 | 35.1 | 69.4 | 40.6 | 39.3 | |
1+2m | 77.8 | 49.8 | 74.9 | 46.4 | 74.0 | 46.0 | 78.2 | 50.2 | 43.1 | |
1+2n | 72.8 | 44.3 | 71.5 | 42.2 | 68.2 | 39.7 | 74.9 | 46.4 | 39.3 | |
1+2o | 83.2 | 55.6 | 82.8 | 55.2 | 75.7 | 48.5 | 85.3 | 57.7 | 46.8 | |
Alcohols | 1+2p | 50.2 | 20.9 | 58.1 | 27.6 | 42.2 | 13.0 | 48.5 | 18.8 | 33.9 |
1+2q | 61.1 | 34.3 | 61.5 | 34.3 | 61.5 | 35.1 | 64.4 | 37.6 | 46.0 | |
Ethers | 1+2r | 45.6 | 17.1 | 48.9 | 20.1 | 45.2 | 16.3 | 47.3 | 19.2 | 33.5 |
1+2s | 53.1 | 23.8 | 53.9 | 25.1 | 49.3 | 21.3 | 53.5 | 25.5 | 33.9 | |
1+2t | 63.6 | 36.8 | 62.7 | 35.5 | 56.4 | 30.1 | 65.7 | 39.3 | 44.3 | |
1+2u | 67.3 | 39.3 | 68.6 | 40.1 | 63.1 | 35.1 | 69.4 | 42.2 | 44.7 |
Table 1 Calculated free-energy barriers obtained by different methods in benzene solution(298.15 K)
Species | Reaction | CAM-B3LYPa | CAM-B3LYPb | M062xa | wB97xa | Expt.c | ||||
---|---|---|---|---|---|---|---|---|---|---|
ΔG≠(g)d/ (kJ·mol-1) | ΔG≠(l)e/ (kJ·mol-1) | ΔG≠(g) / (kJ·mol-1) | ΔG≠(l)/ (kJ·mol-1) | ΔG≠(g)/ (kJ·mol-1) | ΔG≠(l)/ (kJ·mol-1) | ΔG≠(g)/ (kJ·mol-1) | ΔG≠(l)/ (kJ·mol-1) | |||
Amines | 1+2a | 51.0 | 23.0 | 57.3 | 28.4 | 43.1 | 15.1 | 48.5 | 20.5 | 29.7 |
1+2b | 54.4 | 26.3 | 61.1 | 31.8 | 48.1 | 19.7 | 53.9 | 25.5 | 31.4 | |
1+2c | 64.0 | 35.1 | 63.6 | 35.1 | 56.5 | 28.0 | 65.7 | 37.2 | 32.6 | |
1+2d | 55.6 | 27.6 | 66.9 | 38.5 | 53.1 | 24.7 | 54.4 | 26.8 | 27.6 | |
1+2e | 45.6 | 18.4 | 51.4 | 23.8 | 43.5 | 16.3 | 47.3 | 20.5 | 27.6 | |
1+2f | 65.7 | 36.8 | 65.6 | 36.4 | 57.7 | 28.9 | 64.4 | 36.4 | 33.0 | |
1+2g | 70.7 | 43.1 | 68.6 | 40.6 | 63.6 | 36.8 | 72.8 | 45.6 | 33.9 | |
1+2h | 51.4 | 24.3 | 53.1 | 24.7 | 48.5 | 20.1 | 53.9 | 27.2 | 27.2 | |
Hydrocarbons | 1+2i | 67.7 | 38.9 | 76.1 | 47.7 | 54.8 | 26.3 | 64.4 | 35.5 | 36.8 |
1+2j | 66.5 | 37.6 | 69.0 | 39.7 | 59.0 | 30.1 | 68.2 | 38.9 | 35.5 | |
1+2k | 63.6 | 34.7 | 63.1 | 33.9 | 57.7 | 29.3 | 65.2 | 36.8 | 36.0 | |
1+2l | 70.3 | 40.6 | 68.6 | 39.3 | 63.6 | 35.1 | 69.4 | 40.6 | 39.3 | |
1+2m | 77.8 | 49.8 | 74.9 | 46.4 | 74.0 | 46.0 | 78.2 | 50.2 | 43.1 | |
1+2n | 72.8 | 44.3 | 71.5 | 42.2 | 68.2 | 39.7 | 74.9 | 46.4 | 39.3 | |
1+2o | 83.2 | 55.6 | 82.8 | 55.2 | 75.7 | 48.5 | 85.3 | 57.7 | 46.8 | |
Alcohols | 1+2p | 50.2 | 20.9 | 58.1 | 27.6 | 42.2 | 13.0 | 48.5 | 18.8 | 33.9 |
1+2q | 61.1 | 34.3 | 61.5 | 34.3 | 61.5 | 35.1 | 64.4 | 37.6 | 46.0 | |
Ethers | 1+2r | 45.6 | 17.1 | 48.9 | 20.1 | 45.2 | 16.3 | 47.3 | 19.2 | 33.5 |
1+2s | 53.1 | 23.8 | 53.9 | 25.1 | 49.3 | 21.3 | 53.5 | 25.5 | 33.9 | |
1+2t | 63.6 | 36.8 | 62.7 | 35.5 | 56.4 | 30.1 | 65.7 | 39.3 | 44.3 | |
1+2u | 67.3 | 39.3 | 68.6 | 40.1 | 63.1 | 35.1 | 69.4 | 42.2 | 44.7 |
Species | Reaction | k/(L·mol-1·s-1) | |||
---|---|---|---|---|---|
CAM-B3LYP | M062x | wB97x | Expt.[ | ||
Amines | 1+2a | 6.1×108 | 1.4×1010 | 1.5×109 | 4.2×107 |
1+2b | 1.5×108 | 2.1×109 | 2.2×108 | 1.9×107 | |
1+2c | 4.2×106 | 7.5×107 | 1.8×106 | 1.2×107 | |
1+2d | 9.3×107 | 2.7×108 | 1.2×108 | 8.9×107 | |
1+2e | 3.9×109 | 8.9×109 | 1.6×109 | 9.8×107 | |
1+2f | 2.2×106 | 5.6×107 | 2.8×106 | 1.0×107 | |
1+2g | 1.8×105 | 2.2×106 | 6.2×104 | 7.3×106 | |
1+2h | 3.8×108 | 1.8×109 | 1.1×108 | 1.0×108 | |
Hydrocarbons | 1+2i | 9.2×105 | 1.5×108 | 3.6×106 | 2.1×106 |
1+2j | 1.5×106 | 3.3×107 | 1.0×106 | 3.4×106 | |
1+2k | 5.3×106 | 4.8×107 | 2.2×106 | 3.2×106 | |
1+2l | 4.6×105 | 4.3×106 | 4.8×105 | 8.1×105 | |
1+2m | 1.1×104 | 5.6×104 | 9.3×103 | 1.9×105 | |
1+2n | 1.1×105 | 6.8×105 | 4.5×104 | 8.6×105 | |
1+2o | 1.2×103 | 2.0×104 | 5.0×102 | 4.0×104 | |
Alcohols | 1+2p | 1.4×109 | 3.2×1010 | 3.2×109 | 6.9×106 |
1+2q | 6.5×106 | 4.6×106 | 1.5×106 | 5.3×104 | |
Ethers | 1+2r | 6.1×109 | 8.2×109 | 2.7×109 | 7.9×106 |
1+2s | 4.0×108 | 1.1×109 | 2.2×108 | 7.4×106 | |
1+2t | 2.2×106 | 3.3×107 | 8.7×105 | 1.1×105 | |
1+2u | 7.9×105 | 4.2×106 | 2.7×105 | 9.5×104 |
Table 2 Comparison for reaction rate constants obtained by different DFT methods, along with the experimental rate constants at 298.15 K
Species | Reaction | k/(L·mol-1·s-1) | |||
---|---|---|---|---|---|
CAM-B3LYP | M062x | wB97x | Expt.[ | ||
Amines | 1+2a | 6.1×108 | 1.4×1010 | 1.5×109 | 4.2×107 |
1+2b | 1.5×108 | 2.1×109 | 2.2×108 | 1.9×107 | |
1+2c | 4.2×106 | 7.5×107 | 1.8×106 | 1.2×107 | |
1+2d | 9.3×107 | 2.7×108 | 1.2×108 | 8.9×107 | |
1+2e | 3.9×109 | 8.9×109 | 1.6×109 | 9.8×107 | |
1+2f | 2.2×106 | 5.6×107 | 2.8×106 | 1.0×107 | |
1+2g | 1.8×105 | 2.2×106 | 6.2×104 | 7.3×106 | |
1+2h | 3.8×108 | 1.8×109 | 1.1×108 | 1.0×108 | |
Hydrocarbons | 1+2i | 9.2×105 | 1.5×108 | 3.6×106 | 2.1×106 |
1+2j | 1.5×106 | 3.3×107 | 1.0×106 | 3.4×106 | |
1+2k | 5.3×106 | 4.8×107 | 2.2×106 | 3.2×106 | |
1+2l | 4.6×105 | 4.3×106 | 4.8×105 | 8.1×105 | |
1+2m | 1.1×104 | 5.6×104 | 9.3×103 | 1.9×105 | |
1+2n | 1.1×105 | 6.8×105 | 4.5×104 | 8.6×105 | |
1+2o | 1.2×103 | 2.0×104 | 5.0×102 | 4.0×104 | |
Alcohols | 1+2p | 1.4×109 | 3.2×1010 | 3.2×109 | 6.9×106 |
1+2q | 6.5×106 | 4.6×106 | 1.5×106 | 5.3×104 | |
Ethers | 1+2r | 6.1×109 | 8.2×109 | 2.7×109 | 7.9×106 |
1+2s | 4.0×108 | 1.1×109 | 2.2×108 | 7.4×106 | |
1+2t | 2.2×106 | 3.3×107 | 8.7×105 | 1.1×105 | |
1+2u | 7.9×105 | 4.2×106 | 2.7×105 | 9.5×104 |
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