Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs
This work reports the chemoselective polymerization of polar divinyl monomers, including allyl methacrylate (AMA), vinyl methacrylate (VMA), and 4-vinylbenzyl methacrylate (VBMA), by using simple Lewis pairs comprised of homoleptic rare-earth (RE) aryloxide complexes RE(OAr)3 (RE = Sc (1), Y (2), Sm...
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| Format: | Article |
| Language: | English |
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MDPI AG
2018-02-01
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| Series: | Molecules |
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| Online Access: | http://www.mdpi.com/1420-3049/23/2/360 |
| _version_ | 1818995784882847744 |
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| author | Pengfei Xu Lei Wu Liqiu Dong Xin Xu |
| author_facet | Pengfei Xu Lei Wu Liqiu Dong Xin Xu |
| author_sort | Pengfei Xu |
| collection | DOAJ |
| description | This work reports the chemoselective polymerization of polar divinyl monomers, including allyl methacrylate (AMA), vinyl methacrylate (VMA), and 4-vinylbenzyl methacrylate (VBMA), by using simple Lewis pairs comprised of homoleptic rare-earth (RE) aryloxide complexes RE(OAr)3 (RE = Sc (1), Y (2), Sm (3), La (4), Ar = 2,6-tBu2C6H3) and phosphines PR3 (R = Ph, Cy, Et, Me). Catalytic activities of polymerizations relied heavily upon the cooperation of Lewis acid and Lewis base components. The produced polymers were soluble in common organic solvents and often had a narrow molecular weight distribution. A highly syndiotactic poly(allyl methacrylate) (PAMA) with rr ~88% could be obtained by the scandium complex 1/PEt3 pair at −30 °C. In the case of poly(4-vinylbenzyl methacrylate) (PVBMA), it could be post-functionalized with PhCH2SH. Mechanistic study, including the isolation of the zwitterionic active species and the end-group analysis, revealed that the frustrated Lewis pair (FLP)-type addition was the initiating step in the polymerization. |
| first_indexed | 2024-12-20T21:19:21Z |
| format | Article |
| id | doaj.art-48f8df0c16014e9b9edcd6be4f29d29c |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-20T21:19:21Z |
| publishDate | 2018-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-48f8df0c16014e9b9edcd6be4f29d29c2022-12-21T19:26:19ZengMDPI AGMolecules1420-30492018-02-0123236010.3390/molecules23020360molecules23020360Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis PairsPengfei Xu0Lei Wu1Liqiu Dong2Xin Xu3Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, ChinaKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, ChinaKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, ChinaKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, ChinaThis work reports the chemoselective polymerization of polar divinyl monomers, including allyl methacrylate (AMA), vinyl methacrylate (VMA), and 4-vinylbenzyl methacrylate (VBMA), by using simple Lewis pairs comprised of homoleptic rare-earth (RE) aryloxide complexes RE(OAr)3 (RE = Sc (1), Y (2), Sm (3), La (4), Ar = 2,6-tBu2C6H3) and phosphines PR3 (R = Ph, Cy, Et, Me). Catalytic activities of polymerizations relied heavily upon the cooperation of Lewis acid and Lewis base components. The produced polymers were soluble in common organic solvents and often had a narrow molecular weight distribution. A highly syndiotactic poly(allyl methacrylate) (PAMA) with rr ~88% could be obtained by the scandium complex 1/PEt3 pair at −30 °C. In the case of poly(4-vinylbenzyl methacrylate) (PVBMA), it could be post-functionalized with PhCH2SH. Mechanistic study, including the isolation of the zwitterionic active species and the end-group analysis, revealed that the frustrated Lewis pair (FLP)-type addition was the initiating step in the polymerization.http://www.mdpi.com/1420-3049/23/2/360Lewis pairsrare-earthphosphineschemoselective polymerization |
| spellingShingle | Pengfei Xu Lei Wu Liqiu Dong Xin Xu Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs Molecules Lewis pairs rare-earth phosphines chemoselective polymerization |
| title | Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs |
| title_full | Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs |
| title_fullStr | Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs |
| title_full_unstemmed | Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs |
| title_short | Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs |
| title_sort | chemoselective polymerization of polar divinyl monomers with rare earth phosphine lewis pairs |
| topic | Lewis pairs rare-earth phosphines chemoselective polymerization |
| url | http://www.mdpi.com/1420-3049/23/2/360 |
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