Lewis pair polymerization of alkyl methacrylate by amidinato silicon compounds and Tris(pentafluorophenyl)borane
0.5 mol% of the amidinato disilyne [LSi:]2 (1, L = PhC(NtBu)2) and 1 mol% of B(C6F5)3 cooperatively polymerized methyl methacrylate (MMA) to form poly(MMA) with the H and CH2C(=CH2)COMe end groups (P1, Mn = 3.1 ×103 gmol-1; repeating unit, n = 31; polydispersity index, Đ: 1.55). The catalytic mechan...
| Main Authors: | , , , , , |
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| Format: | Journal Article |
| Language: | English |
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2022
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| Online Access: | https://hdl.handle.net/10356/157594 |
| _version_ | 1826120752531767296 |
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| author | Chia, Cher-Chiek Li, Yan Xiao, Longqiang Yang, Ming-Chung Su, Ming-Der So, Cheuk-Wai |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Chia, Cher-Chiek Li, Yan Xiao, Longqiang Yang, Ming-Chung Su, Ming-Der So, Cheuk-Wai |
| author_sort | Chia, Cher-Chiek |
| collection | NTU |
| description | 0.5 mol% of the amidinato disilyne [LSi:]2 (1, L = PhC(NtBu)2) and 1 mol% of B(C6F5)3 cooperatively polymerized methyl methacrylate (MMA) to form poly(MMA) with the H and CH2C(=CH2)COMe end groups (P1, Mn = 3.1 ×103 gmol-1; repeating unit, n = 31; polydispersity index, Đ: 1.55). The catalytic mechanism is proposed, where compound 1 could react with MMA and B(C6F5)3 to form a zwitterionic active species [LSi{CH2C(Me)=C(OMe)O}B(C6F5)3]2. The latter could activate MMA molecules affording poly(MMA) chains on the silicon centers. The methyl group of the last enolate of a poly(MMA) chain on a silicon center could then react with the Si-C bond of the adjacent poly(MMA) chain to form P1, as well as regenerate compound 1 and B(C6F5)3. When compound 1 was replaced by the amidinato amidosilylene [LSiN(SiMe3)2] (2), 1 mol% of compound 2 and 1 mol% of B(C6F5)3 mediated living MMA polymerization in toluene to form the poly(MMA) P2 (Mn = 1.04 ×104 gmol-1; Đ: 1.97). |
| first_indexed | 2024-10-01T05:21:34Z |
| format | Journal Article |
| id | ntu-10356/157594 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T05:21:34Z |
| publishDate | 2022 |
| record_format | dspace |
| spelling | ntu-10356/1575942023-02-28T20:07:00Z Lewis pair polymerization of alkyl methacrylate by amidinato silicon compounds and Tris(pentafluorophenyl)borane Chia, Cher-Chiek Li, Yan Xiao, Longqiang Yang, Ming-Chung Su, Ming-Der So, Cheuk-Wai School of Physical and Mathematical Sciences Science::Chemistry Boranes Carbene Homologues 0.5 mol% of the amidinato disilyne [LSi:]2 (1, L = PhC(NtBu)2) and 1 mol% of B(C6F5)3 cooperatively polymerized methyl methacrylate (MMA) to form poly(MMA) with the H and CH2C(=CH2)COMe end groups (P1, Mn = 3.1 ×103 gmol-1; repeating unit, n = 31; polydispersity index, Đ: 1.55). The catalytic mechanism is proposed, where compound 1 could react with MMA and B(C6F5)3 to form a zwitterionic active species [LSi{CH2C(Me)=C(OMe)O}B(C6F5)3]2. The latter could activate MMA molecules affording poly(MMA) chains on the silicon centers. The methyl group of the last enolate of a poly(MMA) chain on a silicon center could then react with the Si-C bond of the adjacent poly(MMA) chain to form P1, as well as regenerate compound 1 and B(C6F5)3. When compound 1 was replaced by the amidinato amidosilylene [LSiN(SiMe3)2] (2), 1 mol% of compound 2 and 1 mol% of B(C6F5)3 mediated living MMA polymerization in toluene to form the poly(MMA) P2 (Mn = 1.04 ×104 gmol-1; Đ: 1.97). National Research Foundation (NRF) Submitted/Accepted version This work is supported by the National Research Foundation Singapore NRF-ANR (NRF2018-NRF-ANR026 Si-POP). M.-C. Yang and M.-D. Su are grateful to the National Center for High-Performance Computing of Taiwan for generous amounts of computing time, and the Ministry of Science and Technology of Taiwan for the financial support. 2022-05-15T07:48:20Z 2022-05-15T07:48:20Z 2022 Journal Article Chia, C., Li, Y., Xiao, L., Yang, M., Su, M. & So, C. (2022). Lewis pair polymerization of alkyl methacrylate by amidinato silicon compounds and Tris(pentafluorophenyl)borane. European Journal of Organic Chemistry, 2022(13), e202200003-. https://dx.doi.org/10.1002/ejoc.202200003 1434-193X https://hdl.handle.net/10356/157594 10.1002/ejoc.202200003 13 2022 e202200003 en NRF2018-NRF-ANR026 Si-POP European Journal of Organic Chemistry This is the peer reviewed version of the following article: Chia, C., Li, Y., Xiao, L., Yang, M., Su, M. & So, C. (2022). Lewis pair polymerization of alkyl methacrylate by amidinato silicon compounds and Tris(pentafluorophenyl)borane. European Journal of Organic Chemistry, 2022(13), e202200003-, which has been published in final form at https://doi.org/10.1002/ejoc.202200003. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. application/pdf |
| spellingShingle | Science::Chemistry Boranes Carbene Homologues Chia, Cher-Chiek Li, Yan Xiao, Longqiang Yang, Ming-Chung Su, Ming-Der So, Cheuk-Wai Lewis pair polymerization of alkyl methacrylate by amidinato silicon compounds and Tris(pentafluorophenyl)borane |
| title | Lewis pair polymerization of alkyl methacrylate by amidinato silicon compounds and Tris(pentafluorophenyl)borane |
| title_full | Lewis pair polymerization of alkyl methacrylate by amidinato silicon compounds and Tris(pentafluorophenyl)borane |
| title_fullStr | Lewis pair polymerization of alkyl methacrylate by amidinato silicon compounds and Tris(pentafluorophenyl)borane |
| title_full_unstemmed | Lewis pair polymerization of alkyl methacrylate by amidinato silicon compounds and Tris(pentafluorophenyl)borane |
| title_short | Lewis pair polymerization of alkyl methacrylate by amidinato silicon compounds and Tris(pentafluorophenyl)borane |
| title_sort | lewis pair polymerization of alkyl methacrylate by amidinato silicon compounds and tris pentafluorophenyl borane |
| topic | Science::Chemistry Boranes Carbene Homologues |
| url | https://hdl.handle.net/10356/157594 |
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