自由基的热力学和动力学定量参数

doi:10.6023/cjoc202106018

有机化学 ›› 2021, Vol. 41 ›› Issue (10): 3892-3902.DOI: 10.6023/cjoc202106018 上一篇下一篇

所属专题：南开大学化学学科创立100周年；热点论文虚拟合集

综述与进展

自由基的热力学和动力学定量参数

黄谋新^a, 贾宗宾^b^,^c, 罗三中^a^,^b^,^c^,^*(), 程津培^a^,^d^,^*()

a 清华大学化学系基础分子科学中心北京 100084
b 中国科学院化学研究所分子识别与功能重点实验室北京 100190
c 中国科学院大学北京 100490
d 南开大学化学学院元素有机化学国家重点实验室天津 300071

收稿日期:2021-06-08 修回日期:2021-06-27 发布日期:2021-07-12
通讯作者: 罗三中, 程津培
作者简介:
† 共同第一作者
基金资助:
国家自然科学基金(21672217); 国家自然科学基金(21861132003); 国家自然科学基金(22031006)

Quantitative Thermodynamic and Kinetic Parameters of Radical

Mouxin Huang^a, Zongbin Jia^b^,^c, Sanzhong Luo^a^,^b^,^c(), Jin-Pei Cheng^a^,^d()

a Center for Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084
b Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190
c University of Chinese Academy of Sciences, Beijing 100490
d State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071

Received:2021-06-08 Revised:2021-06-27 Published:2021-07-12
Contact: Sanzhong Luo, Jin-Pei Cheng
About author:
† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21672217); National Natural Science Foundation of China(21861132003); National Natural Science Foundation of China(22031006)

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摘要/Abstract

近十余年来, 自由基化学重新焕发了生机, 在合成化学和材料科学等领域取得了突破性的进展. 与突飞猛进的合成方法学研究相比, 人们对自由基反应的机制以及规律的研究和总结相对滞后. 另一方面, 自由基一直是物理有机化学领域重要的研究对象, 在横跨一个世纪的研究历程中积累了大量热力学和动力学参数, 但这些数据大多数都淹没在文献中, 缺乏系统的汇编和整理, 从而不被大多数合成化学家所熟知. 本综述拟对自由基热力学和动力学定量参数进行系统的汇编和整理, 以期为相关领域的理性设计与发展提供支撑数据. 这些数据参数主要包括自由基稳定化能(RSE)、自由基寿命(τ)、取代基常数(σ)、亲电性指数(ω)等. 以这些数据为基础, 将梳理一些重要的自由基化学基本概念如自由基稳定性、Class S/O自由基取代基效应、稳态和瞬态自由基效应等

关键词: 自由基性质, 定量参数, 稳定性, 取代基效应, 稳态自由基效应

Radical chemistry has gained its renaissence in the past decade and trendendous progresses have been witnessed in synthetic and material chemistry. However, mechanism studies are largely lagging behind comparing with rapid paces in the development of synthetic methodologies. On the other hand, the study of radical species remains a central theme in physial organic chemistry, and a large amount of thermodynamic and kinetic data on radicals have been generated over a century's reserch. Unfortuately, there has been no systematic compilation and curation of these quatitative data that are dispersedly distributed and buried in literature. As a result, most synthetic chemists are not acquainted with these valuable data. In this review, we aim in compiling and curating thermodynamic and kinetic parameters of radicals, that may hopefully provide a quantitative data basis for rational development and evolution of radical chemistry. The key parameters include radical stability energy (RSE), radical lifetime (τ), substituent constant (σ) and electrophilic index (ω). Fundamental concepts such as radical stability, Class S/O radical substitution effect, persistent/transient radical effect will be discussed on the basis of data.

Key words: radical property, quantitative parameters, stability, substituent effect, persistent radical effect

引用此文

黄谋新, 贾宗宾, 罗三中, 程津培. 自由基的热力学和动力学定量参数[J]. 有机化学, 2021, 41(10): 3892-3902.

Mouxin Huang, Zongbin Jia, Sanzhong Luo, Jin-Pei Cheng. Quantitative Thermodynamic and Kinetic Parameters of Radical[J]. Chinese Journal of Organic Chemistry, 2021, 41(10): 3892-3902.

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参考文献 70

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Substituent	ArCH₃		ArCH₂CN		ArCH(CN)CO₂Et
Substituent	BDE	RSE^a	BDE	RSE	BDE	RSE
4-OMe	362.2	6.0	337.1	6.3	327.9	8.4
4-Me	366.6	1.6	340.9	2.5	334.8	1.5
H	368.2	(0)	343.4	(0)	336.3	(0)
4-CO₂Me	—	—	346.6	–3.2	343.2	–6.9
4-CN	388.0	0.2	345.4	–2.0	348.1	–11.8
Substituent (E⁺)	Ph-CH₂-E⁺		Ph-COCH₂-E⁺		9-E⁺-fluorene
Substituent (E⁺)	BDE	RSE	BDE	RSE	BDE	RSE
H	370.5	(0)	388.9	(0)	332.5	(0)
Ph₃P⁺	370.9	–0.4	403.6	–14.6	341.3	–8.8
(n-Bu)₃P⁺	373.0	–2.5	406.5	–17.6	347.1	–14.6
Me₃N⁺	379.7	–9.2	404.8	–15.9	355.1	–22.6
Ph₃As⁺	383.5	–13.0	400.2	–11.3	345.4	–13.0
Substituent	ArNH₂		ArNHCOMe		ArC(Me)=NNHCONH₂
Substituent	BDE	RSE	BDE	RSE	BDE	RSE
4-OMe	378.2	8.0	400.1	15.4	381.0	3.2
4-Me	384.9	1.3	408.0	7.5	382.6	1.6
H	386.2	(0)	415.5	(0)	384.2	(0)
4-CN	398.3	–12.1	424.8	–9.3	388.2	–4.0
4-NO₂	404.6	–18.4	427.5	–12.0	387.2	–3.0
Substituent	ArNHPh		ArNHNH₂		ArNHOH
Substituent	BDE	RSE	BDE	RSE	BDE	RSE
4-Me	365	2	302	3	284	8
H	367	(0)	305	(0)	292	(0)
4-CN	—	—	326	–21	—	—
Substituent	ArNHPO(OEt)₂		ArNH(P⁺Ph₃)
Substituent	BDE	RSE	BDE	RSE
4-Me	391	6	288	–2
H	397	(0)	286	(0)
4-CN	414	–17	271	15

Substituent	ArCH₃		ArCH₂CN		ArCH(CN)CO₂Et
Substituent	BDE	RSE^a	BDE	RSE	BDE	RSE
4-OMe	362.2	6.0	337.1	6.3	327.9	8.4
4-Me	366.6	1.6	340.9	2.5	334.8	1.5
H	368.2	(0)	343.4	(0)	336.3	(0)
4-CO₂Me	—	—	346.6	–3.2	343.2	–6.9
4-CN	388.0	0.2	345.4	–2.0	348.1	–11.8
Substituent (E⁺)	Ph-CH₂-E⁺		Ph-COCH₂-E⁺		9-E⁺-fluorene
Substituent (E⁺)	BDE	RSE	BDE	RSE	BDE	RSE
H	370.5	(0)	388.9	(0)	332.5	(0)
Ph₃P⁺	370.9	–0.4	403.6	–14.6	341.3	–8.8
(n-Bu)₃P⁺	373.0	–2.5	406.5	–17.6	347.1	–14.6
Me₃N⁺	379.7	–9.2	404.8	–15.9	355.1	–22.6
Ph₃As⁺	383.5	–13.0	400.2	–11.3	345.4	–13.0
Substituent	ArNH₂		ArNHCOMe		ArC(Me)=NNHCONH₂
Substituent	BDE	RSE	BDE	RSE	BDE	RSE
4-OMe	378.2	8.0	400.1	15.4	381.0	3.2
4-Me	384.9	1.3	408.0	7.5	382.6	1.6
H	386.2	(0)	415.5	(0)	384.2	(0)
4-CN	398.3	–12.1	424.8	–9.3	388.2	–4.0
4-NO₂	404.6	–18.4	427.5	–12.0	387.2	–3.0
Substituent	ArNHPh		ArNHNH₂		ArNHOH
Substituent	BDE	RSE	BDE	RSE	BDE	RSE
4-Me	365	2	302	3	284	8
H	367	(0)	305	(0)	292	(0)
4-CN	—	—	326	–21	—	—
Substituent	ArNHPO(OEt)₂		ArNH(P⁺Ph₃)
Substituent	BDE	RSE	BDE	RSE
4-Me	391	6	288	–2
H	397	(0)	286	(0)
4-CN	414	–17	271	15

Substituent	τ_p	E_R	E_D	E_R^N	σ_F•	σ_C•	σ_J•	σ_α•
H	0	0	0	0	0	0	0	0
p-NO₂	0.90	0.41	0.27	0.41	0.27		0.76
p-N=NPh	0.90				0.33
p-NMe₂		0.24		–0.11
p-Ph							0.42
p-COMe		0.24		0.24	0.12			0.066
p-COPh								0.064
p-CN		0.24	0.32	0.23	0.53	0.46		0.043
p-SMe					0.34	0.43
p-CO₂Me						0.35		0.048
p-SOMe								0.006
p-SO₃Me								0.003
p-OCOMe								0.001
p-OMe	0.14	0.11	0.19	–0.008	–0.12	0.24	0.42	0.034
p-SiMe₃						0.17
p-Br		0.12		0.072	0.17	0.14
p-^tBu		0.03		0.014		0.13		0.036
p-ⁱPr		0.03		0.034
p-F								–0.011
p-Cl	0.16	0.10	0.07	0.062	0.08	0.12	0.18	0.017
p-I		0.12		0.037	0.16
p-OPh		0.13		–0.147
p-Me	0.09	0.03	0.11	–0.020	–0.02	0.11	0.39	0.015
p-CF₃						0.08		0.001
m-SiMe₃						0.03
m-Me						–0.02		–0.001
m-CO₂Me								–0.004
m-OMe						–0.02
m-Cl						–0.04		–0.001
m-F						–0.05
m-CF₃						–0.07		–0.014
m-F						–0.08		–0.018
m-CN						–0.12		–0.039
m-OPh								–0.013

Substituent	τ_p	E_R	E_D	E_R^N	σ_F•	σ_C•	σ_J•	σ_α•
H	0	0	0	0	0	0	0	0
p-NO₂	0.90	0.41	0.27	0.41	0.27		0.76
p-N=NPh	0.90				0.33
p-NMe₂		0.24		–0.11
p-Ph							0.42
p-COMe		0.24		0.24	0.12			0.066
p-COPh								0.064
p-CN		0.24	0.32	0.23	0.53	0.46		0.043
p-SMe					0.34	0.43
p-CO₂Me						0.35		0.048
p-SOMe								0.006
p-SO₃Me								0.003
p-OCOMe								0.001
p-OMe	0.14	0.11	0.19	–0.008	–0.12	0.24	0.42	0.034
p-SiMe₃						0.17
p-Br		0.12		0.072	0.17	0.14
p-^tBu		0.03		0.014		0.13		0.036
p-ⁱPr		0.03		0.034
p-F								–0.011
p-Cl	0.16	0.10	0.07	0.062	0.08	0.12	0.18	0.017
p-I		0.12		0.037	0.16
p-OPh		0.13		–0.147
p-Me	0.09	0.03	0.11	–0.020	–0.02	0.11	0.39	0.015
p-CF₃						0.08		0.001
m-SiMe₃						0.03
m-Me						–0.02		–0.001
m-CO₂Me								–0.004
m-OMe						–0.02
m-Cl						–0.04		–0.001
m-F						–0.05
m-CF₃						–0.07		–0.014
m-F						–0.08		–0.018
m-CN						–0.12		–0.039
m-OPh								–0.013

Substituent	σ_mb	σ_JJ•	Substituent	σ_mb	σ_JJ•
H	0	0	p-OMe	–0.77	0.23
p-NMe₂	–0.96	1.00	p-Br	0.13	0.23
p-CF=CF₂	0.40	0.86	p-Cl	0.11	0.22
p-SMe	–0.18	0.62	p-CH=CH₂	0.03
p-COMe	0.56	0.54	p-Me	–0.29	0.15
p-SOMe	0.19	0.50	p-Et		0.15
p-Ph	0.06	0.47	p-CF₃	0.49	–0.01
p-CN	0.86	0.42	p-F	–0.24	–0.02
p-COOH	0.31	0.38	m-Me	–0.20	0
p-CONH₂	0.10	0.38	m-Br	0.36	0.12
p-SO₂Me	0.64	0.41	m-^tBu	–0.20	0.11
p-NO₂	0.86	0.36	m-CN	0.89	0.11
p-OCOMe	-0.14	0.35	m-OMe	–0.11	0.10
p-CO₂Me	0.48	0.33	m-CO₂Me	0.21	0.10
p-SO₂Me	0.64	0.41	m-Et	–0.15
p-SiMe₃	0.14	0.31	m-F	0.23	0.03
p-^cPr	–0.31	0.29	m-NO₂	0.69	0.001
p-^tBu	–0.22	0.26	m-Cl	0.12	–0.05
p-OPh	–0.46		m-CF₃	0.39	–0.07

自由基的热力学和动力学定量参数

Quantitative Thermodynamic and Kinetic Parameters of Radical

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Substituent	log K	M(H₂O)
·H	4.70	1.47
·OH	4.33	1.10
·CH₃	3.23	0.00
·CF₃	4.18	0.95
·CCl₃	4.23	1.00
·CH₂OH	2.48	–0.75
·CH₂CH₂OH	2.00	–1.23
·C(CH₃)₂OH	2.00	–1.23
·CH₂C(OH)(CH₃)₂	3.60	0.37

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