Progress in Rare-Earth Metal-Based Lewis Pair Chemistry

doi:10.6023/cjoc202112008

Abstract

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

Cite this article

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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Fig. & Tab. 20

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

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

Scheme 3. Reactions of complexes 9 with benzaldehyde and isocyanate

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

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

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

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

Scheme 8. Reactions of complexes 24 with CO2

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

Scheme 10. Reactions of complex 9a with diazo compounds

Scheme 11. Reactions of RE complexes 31 with azides

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

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

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

Scheme 15. Isospecific polymerization of MMA with RE complexes

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

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

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

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

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

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