Quantitative Thermodynamic and Kinetic Parameters of Radical

doi:10.6023/cjoc202106018

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (10): 3892-3902.DOI: 10.6023/cjoc202106018 Previous Articles Next Articles

Special Issue: 南开大学化学学科创立100周年；热点论文虚拟合集

REVIEWS

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)

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

Cite this article

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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Fig. & Tab. 17

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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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Fig. & Tab. 17

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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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