基于稀土金属路易斯酸碱对化学的研究进展

doi:10.6023/cjoc202112008

摘要/Abstract

近年来, 利用稀土金属作为路易斯酸, 与主族路易斯碱组合的路易斯酸碱对得到了开发. 这类酸碱对组合通过路易斯酸与路易斯碱协同作用, 从而实现底物的活化, 展示了与传统稀土金属配合物不同的活化模式. 其可以与氢气反应, 断裂非极性的氢-氢键; 也能够与羰基类、重氮类及叠氮类等不饱和小分子反应, 得到一系列结构独特的稀土金属配合物. 同时这类路易斯酸碱对也可以用于催化极性烯烃聚合反应、二氧化碳硅氢化还原反应中, 展现出优异的催化性能. 综述了上述研究结果, 并对该领域的发展趋势和前景进行了展望.

关键词: 稀土金属, 路易斯酸碱对, 氢气活化, 聚合反应, 二氧化碳还原

Rare-earth (RE) metal-base Lewis pairs comprised of Lewis acidic RE metals and main group Lewis bases have been developed recently. Distinct from traditional reaction pathway mediated by RE metal complexes, it’s the synergistic effect between Lewis acidic RE metal center and Lewis basic center that enables the activation of incoming substrates. This kind of extraordinary Lewis pairs can split the non-polar H-H bond, as well as react with carbonyl compounds, diazo compounds, azide compounds, etc., leading to a series of unique and intriguing RE metal complexes. Meanwhile, these Lewis pairs are also applied as catalysts for polymerization of conjugated polar alkenes and hydrosilylation of carbon dioxide with excellent results. Researches mentioned above are reviewed in this paper, and new prospects for the future development of RE based Lewis pairs are put forward.

Key words: rare-earth metal, Lewis pair, dihydrogen activation, polymerization, CO₂ reduction

引用此文

管怡雯, 常克俭, 孙千林, 徐信. 基于稀土金属路易斯酸碱对化学的研究进展[J]. 有机化学, 2022, 42(5): 1326-1335.

Yiwen Guan, Kejian Chang, Qianlin Sun, Xin Xu. Progress in Rare-Earth Metal-Based Lewis Pair Chemistry[J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1326-1335.

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图/表 20

图式1. RE(OAr)3/NHC路易斯酸碱对与氢气的反应

Scheme 1. Reactions of RE(OAr)3/NHC Lewis pairs with dihydrogen

图式2. 阳离子型稀土配合物与α,β-不饱和酮、芳香醛的反应

Scheme 2. Reactions of cationic RE complexes with α,β-unsaturated carbonyl compounds and aromatic aldehydes

图式3. 配合物9与苯甲醛和异氰酸酯的反应

Scheme 3. Reactions of complexes 9 with benzaldehyde and isocyanate

图式4. 配合物9a与共轭羰基类化合物的反应

Scheme 4. Reactions of complex 9a with conjugated carbonyl compounds

图式5. 稀土金属/钯杂双金属配合物与二苯乙烯酮的反应

Scheme 5. Reactions of heterobimetallic RE/Pd complexes with diphenylethylenone

图式6. 铈/磷路易斯酸碱对与异氰酸酯和异硫氰酸酯的反应

Scheme 6. Reactions of Ce/P Lewis pairs with isocyanate and isothiocyanate

图式7. 钪烷氧基配合物22与CO2的反应

Scheme 7. Reaction of scandium N-heterocyclic carbene complex 22 with CO2

图式8. 配合物24与CO2的反应

Scheme 8. Reactions of complexes 24 with CO2

图式9. La(OAr)3/NHC路易斯酸碱对与CO2的反应

Scheme 9. Reaction of La(OAr)3/NHC Lewis pair with CO2

图式10. 配合物9a与重氮化合物的反应

Scheme 10. Reactions of complex 9a with diazo compounds

图式11. 稀土配合物31与叠氮化合物的反应

Scheme 11. Reactions of RE complexes 31 with azides

图式12. 基于RE(OAr)3路易斯酸碱对与Me3SiN3的反应

Scheme 12. Reactions of RE(OAr)3 based Lewis pairs with Me3SiN3

图式13. 铈/磷配合物19与重氮、叠氮小分子的反应

Scheme 13. Reactions of Ce/P complex 19 with diazo and azide compounds

图式14. 稀土金属/磷路易斯酸碱对催化MMA及其环状衍生物的聚合

Scheme 14. Polymerization of MMA and its cyclic derivatives with RE/P Lewis pairs

图式15. 稀土金属配合物催化MMA的等规聚合

Scheme 15. Isospecific polymerization of MMA with RE complexes

图式16. RE(OAr)3/PR3路易斯酸碱对催化极性共轭烯烃的聚合

Scheme 16. Polymerization of conjugated polar alkenes with RE(OAr)3/PR3 Lewis pairs

图式17. RE(OAr)3/PR3路易斯酸碱对催化极性双乙烯基烯烃的聚合及后官能团化

Scheme 17. Polymerization of polar divinyl monomers with RE(OAr)3/PR3 Lewis pairs and post-functionalization reaction

图式18. RE(OAr)3/YPhos路易斯酸碱对催化4VP及其衍生物的聚合

Scheme 18. Polymerization of 4VP and its derivatives with RE(OAr)3/YPhos Lewis pairs

图式19. 稀土金属离子对[Cp*2Sc]+[HB(C6F5)3]–与CO2的反应

Scheme 19. Reaction of [Cp*2Sc]+[HB(C6F5)3]– with CO2

图式20. RE(OAr)3/B(C6F5)3催化CO2的硅氢化还原

Scheme 20. Hydrosilylation of CO2 by the combination of RE(OAr)3 and B(C6F5)3

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