Synthesis of N-confused Porphyrin Manganese, Iron and Cobalt Complexes and Their Applications

doi:10.6023/A24020052

Acta Chimica Sinica ›› 2024, Vol. 82 ›› Issue (5): 541-550.DOI: 10.6023/A24020052 Previous Articles Next Articles

Review

N-错位卟啉锰、铁和钴配合物的合成及其应用

李万红^a, 穆应红^a, 王新^a, 李星^a, 刘海洋^b, 彭素红^a^,^*()

a 宜春学院化学与生物工程学院宜春 336000
b 华南理工大学化学系广州 510641

投稿日期:2024-02-15 发布日期:2024-04-11

作者简介:

李万红, 就读于宜春学院化学与生物工程学院, 2021级药学专业硕士生, N-错位卟啉金属配合物的合成及应用研究.

穆应红, 就读于宜春学院化学与生物工程学院, 2023级药学专业硕士生, N-错位卟啉金属配合物的合成及应用研究.

王新, 就读于宜春学院化学与生物工程学院, 2020级化学专业本科生, N-错位卟啉金属配合物的合成及应用研究.

李星, 就读于宜春学院化学与生物工程学院, 2017级应用化学本科生, N-错位卟啉金属配合物的合成及应用研究.

刘海洋, 1997年博士毕业于中山大学化学专业, 现任华南理工大学化学与化工学院教授. 广东省高等学校“千百十工程”第三批培养对象. 广东省化学会无机化学专业委员会委员. 长期致力于金属卟啉类大环化合物的催化, 光动力抗肿瘤, 超快速光物理化学过程, 电催化材料与燃料电池研究.

彭素红, 2016年博士毕业于华南理工大学无机化学专业. 现任宜春学院化学与生物工程学院副教授. 主要研究方向为N-错位卟啉金属配合物的合成及应用研究.

基金资助:
国家自然科学基金(21671068); 宜春学院2018地方发展研究中心项目(DF2018021); 江西省教育厅科学技术项目(GJJ2201723); 江西省教育厅科学技术项目(GJJ2201724); 江西省卫生健康委科技计划项目(202212701); 绿色化工技术福建省高校重点实验室开放基金(WYKF-GCT2022-1)

Synthesis of N-confused Porphyrin Manganese, Iron and Cobalt Complexes and Their Applications

Wanhong Li^a, Yinghong Mu^a, Xin Wang^a, Xing Li^a, Haiyang Liu^b, Suhong Peng^a()

a College of Chemsitry and Bioengineering, Yichun University, Yichun 336000, China
b Department of Chemistry, South China University of Technology, Guangzhou 510641, China

Received:2024-02-15 Published:2024-04-11
Contact: *E-mail: shpeng1987@163.com
Supported by:
National Natural Science Foundation of China(21671068); 2018 local Development Research Center Project of Yichun Univeristy(DF2018021); Science and Technology Research Project of Education Comission of Jiangxi Province(GJJ2201723); Science and Technology Research Project of Education Comission of Jiangxi Province(GJJ2201724); science and technology research project of health commission of Jiangxi province(202212701); Open Fund of Key Laboratory of Green Chemical Technology of Fujian Province University(WYKF-GCT2022-1)

Study on the synthesis and applications of N-confused porphyrin manganese, iron and cobalt complexes has become one of the hot topics of porphyrin chemistry. Compared with the coordination chemistry of porphyrin, that of N-confused porphyrin is complicated because of the peripheral nitrogen atom, the intramolecular C—H bond and NH tautomerism. N-confused porphyrin has two NH tautomers, isomer A and isomer B. Varied functions are observed in the coordination chemistry of N-confused porphyrin such as stabilization of unusual metal oxidation states and metal-carbon bond formation. N-confused porphyrins have flexible character toward the metal oxidation state. Removal of the number of hydrogen atoms from one to three will result in a monanionic, dianionic and trianionic macrocycle. The various metal oxidation states are observed in N-confused porphyrin manganese, iron and cobalt complexes. The monovalent character of N-confused porphyrin is observed in cobalt chemistry such as Co^II(2-N-RNCTPP)Cl and Co^II(NCTPP). The cobalt metal takes a valence of +2 since Co^II(2-N-RNCTPP)Cl has a monoanionic axial ligand and N-confused porphyrin ligand. The squar-planar Co(Ⅱ) complex Co^II(NCTPP) exists the cobalt-carbon bond. The divalent and trivalent characters of N-confused porphyrins are observed in manganese, iron and cobalt chemistry. In Mn(Ⅱ) and Fe(Ⅱ) complexes of N-confused porphyrin Mn^II(NHCTPP)Br and Fe^II(NHCTPP)Br, oxidation of the metal center is observed through intramolecular C—H bond activation of N-confused porphyrin ligand, which can be converted into Mn(Ⅲ) and Fe(Ⅲ) complexes Mn^Ⅲ(NCTPP)Br and Fe^Ⅲ(NCTPP)Br on exposure to air in solutions. {FeNO}⁶ with a linear Fe-NO conformation is observed in the iron chemistry of N-confused porphyrin, which is unusually stable among the porphyrin iron nitrosyl complexes. It implies that iron N-confused porphyrin complexes can be used to study NO delivery and storage. This review covers the progress on the synthesis of N-confused porphyrin manganese, iron and cobalt complexes and their applications in the field of catalytic chemistry and biological chemistry. The synthesis methods of N-confused porphyrin manganese, iron and cobalt complexes and their applications in catalytic oxidation, cyclopropanation of alkene, nitrate reductase activity and chemical nuclease activity are introduced systematically.

Key words: N-confused porphyrin manganese, iron and cobalt complexes, synthesis, application

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Wanhong Li, Yinghong Mu, Xin Wang, Xing Li, Haiyang Liu, Suhong Peng. Synthesis of N-confused Porphyrin Manganese, Iron and Cobalt Complexes and Their Applications[J]. Acta Chimica Sinica, 2024, 82(5): 541-550.

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Fig. & Tab. 19

Figure 1. Molecular structures of isomer A and isomer B of tetraphenyl N-confused porphyrin

配合物	反应条件	产率
Mn^II(NHCTPP)Br	氮气保护下, 以乙腈和四氢呋喃的混合溶剂作为反应溶剂, 以四苯基N-错位卟啉与溴化锰为原料, 再加入二甲基吡啶, 回流反应.	82%
Mn^III(2-N-RNCTPP)Br	空气条件下, 以二氯甲烷与甲醇的混合溶液作为反应溶剂, 2-N-烷基四苯基N-错位卟啉与溴化锰回流反应.	61%
Fe^II(NHCTPP)Br	无氧条件下, 以乙腈和四氢呋喃的混合溶剂作为反应溶剂, 以四苯基N-错位卟啉与溴化亚铁为原料, 再加入二甲基吡啶, 回流反应.	85%
Co^II(2-N-RNCTPP)Cl	空气条件下, 以乙腈和甲苯的混合溶剂作为反应溶剂, 加入N-烷基化的N-错位卟啉与六水合氯化钴, 回流反应.	26%

Table 1. Synthesis of N-confused porphyrin manganese, iron and cobalt complexes

Figure 2. Synthetic route of N-confused porphyrin manganese complexes

Figure 3. UV-visible spectra of MnII(NHCTPP)Br and MnIII(NCTPP)Br

Figure 4. Crystal structures of MnII(NHCTPP)Br and MnIII(NCTPP)Br

Figure 5. Synthetic route of 2-N-alkyl tetraphenyl N-confused porphyrin manganese complexes

Figure 6. Synthetic route of N-confused porphyrin iron(II) complexes [FeII(NHCTPP)Br] and N-confused porphyrin iron(III) complexes [FeIII(NCTPP)Br]

Figure 7. Crystal structures of FeII(NHCTPP)Br and FeIII(NCTPP)Br

Figure 8. Synthetic route of N-confused porphyrin cobalt(III) complex CoIII(NCTPP)(H2O)

Figure 9. Crystal structures of CoIII(NCTPP)(H2O) and CoIII(NCTPP)py2

Figure 10. Synthetic route of N-confused porphyrin cobalt(II) complex CoII(NCTPP)

Figure 11. Synthetic route of N-confused porphyrin cobalt(II) complexes CoII(NCTPP)py and N-confused porphyrin cobalt(III) complexes CoIII(NCTPP)py2

Figure 12. Synthetic route of N-confused porphyrin cobalt(II) chloride complexes

Figure 13. Molecular structures of N-confused porphyrin manganese complexes MnIII(2-N-CH3-NCTArP)Cl

Figure 14. Molecular structures of iron tetraphenyl N-confused porphyrin complexes {FeNO}6 and {FeNO}7

Figure 15. Molecular structures of CoII(NCTPP)py and CoII(2-N-CH3NCTPP)py

Catalyst(mol%)	n_Styrene/ n_EDA	Temp./ Time	Yield	trans/cis
Co^IITPP(0.5)	5/1	r.t./1 h	6%	72/28
Co^IITPP(1)	1/1.2	80 ℃/20 h	67%	74/26
Co^II(NCTPP)py(1)	1/1.2	80 ℃/20 h	35%	98/2
Co^II(2-N-CH₃NCTPP) py(1)	1/1.2	80 ℃/20 h	51%	98/2
	1/1.2	r.t./20 h	85%	93/7
	5/1	80 ℃/20 h	76.5%	91/9
Co^II(2-N-CH₃NCTPP) py(0.5)	5/1	r.t./1 h	31%	92/8
7(0.5)	5/1	80 ℃/6 h	70%	83/17
7-_red(0.1)	5/1	r.t./1 h	39%	89/11
7-_red(0.5)	5/1	r.t./1 h	80%	92/8
8_-red(0.5)	5/1	r.t./1 h	76%	90/10

Table 2. Catalytic activities of N-confused cobalt porphyrin complexes on the cyclopropanation of styrene

Figure 16. Molecular structures of cobalt(III) N-confused porphyrin complexes 7 and 8

Figure 17. Molecular structures of cobalt N-confused porphyrin complexes {Co(NO)}8 and {Co(NO)}9

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N-错位卟啉锰、铁和钴配合物的合成及其应用

Synthesis of N-confused Porphyrin Manganese, Iron and Cobalt Complexes and Their Applications

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