Lewis Pair Polymerization of Alkyl Methacrylate by Amidinato Silicon Compounds and Tris(pentafluorophenyl)borane

Cher Chiek Chia; Yan Li; Longqiang Xiao; Ming Chung Yang; Ming Der Su; Cheuk Wai So

doi:10.1002/ejoc.202200003

Lewis Pair Polymerization of Alkyl Methacrylate by Amidinato Silicon Compounds and Tris(pentafluorophenyl)borane

Cher Chiek Chia, Yan Li, Longqiang Xiao, Ming Chung Yang, Ming Der Su, Cheuk Wai So^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

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, M_n=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 (M_n=1.04×10⁴ gmol⁻¹; Đ: 1.97).

Original language	English
Article number	e202200003
Journal	European Journal of Organic Chemistry
Volume	2022
Issue number	13
DOIs	https://doi.org/10.1002/ejoc.202200003
Publication status	Published - Apr 5 2022
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry

Keywords

Boranes
Carbene homologues
Methacrylate
Polymerization
Silicon

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10.1002/ejoc.202200003

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@article{e3625e1342b04f5bbe4242156f94b978,

title = "Lewis Pair Polymerization of Alkyl Methacrylate by Amidinato Silicon Compounds and Tris(pentafluorophenyl)borane",

abstract = "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, {\D}: 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; {\D}: 1.97).",

keywords = "Boranes, Carbene homologues, Methacrylate, Polymerization, Silicon",

author = "Chia, {Cher Chiek} and Yan Li and Longqiang Xiao and Yang, {Ming Chung} and Su, {Ming Der} and So, {Cheuk Wai}",

note = "Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

year = "2022",

month = apr,

day = "5",

doi = "10.1002/ejoc.202200003",

language = "English",

volume = "2022",

journal = "European Journal of Organic Chemistry",

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number = "13",

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TY - JOUR

T1 - Lewis Pair Polymerization of Alkyl Methacrylate by Amidinato Silicon Compounds and Tris(pentafluorophenyl)borane

AU - Chia, Cher Chiek

AU - Li, Yan

AU - Xiao, Longqiang

AU - Yang, Ming Chung

AU - Su, Ming Der

AU - So, Cheuk Wai

PY - 2022/4/5

Y1 - 2022/4/5

N2 - 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).

AB - 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).

KW - Boranes

KW - Carbene homologues

KW - Methacrylate

KW - Polymerization

KW - Silicon

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U2 - 10.1002/ejoc.202200003

DO - 10.1002/ejoc.202200003

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SN - 1434-193X

VL - 2022

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 13

M1 - e202200003

ER -

Lewis Pair Polymerization of Alkyl Methacrylate by Amidinato Silicon Compounds and Tris(pentafluorophenyl)borane

Abstract

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ASJC Scopus Subject Areas

Keywords

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