Generation of High‐Molecular‐Weight Polymers with Diverse Substituents: An Unusual Metal‐Free Synthesis of Poly(aminoborane)s

Staubitz, Anne

doi:10.1002/anie.201801903

Cited by 9 publications

(7 citation statements)

References 18 publications

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“…The synthesis of polyaminoboranes (HRBNR′H) n , polymers with alternating B−N main‐chain units, has attracted considerable interest since the groundbreaking report in 2008 by Manners and co‐workers of the catalyzed dehydropolymerization of H 3 B⋅NMeH 2 to produce high molecular weight, soluble, polymers (Scheme ) . In the ten years since, considerable progress has been made in understanding and developing this methodology for the synthesis of main‐group polymeric materials . Challenges remain, however, in both fundamental mechanistic understanding and translating this to the production of tailored new materials.…”

Section: Introductionmentioning

confidence: 99%

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Amine–Borane Dehydropolymerization: Challenges and Opportunities

Colebatch

Weller

2018

Chemistry A European J

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The dehydropolymerization of amine–boranes, exemplified as H 2 RB⋅NR′H 2 , to produce polyaminoboranes (HRBNR′H) n that are inorganic analogues of polyolefins with alternating main‐chain B−N units, is an area with significant potential, stemming from both fundamental (mechanism, catalyst development, main‐group hetero‐cross‐coupling) and technological (new polymeric materials) opportunities. This Concept article outlines recent advances in the field, covering catalyst development and performance, current mechanistic models, and alternative non‐catalytic routes for polymer production. The substrate scope, polymer properties and applications of these exciting materials are also outlined. Challenges and opportunities in the field are suggested, as a way of providing focus for future investigations.

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Section: Introductionmentioning

confidence: 99%

“…[1,2] In the ten years since, considerable progress has been made in understanding and developing this methodology for the synthesis of main-group polymericm aterials. [3][4][5][6][7][8] Challenges remain, however,i nb oth fundamental mechanistic understanding and translating this to the production of tailored new materials.…”

Section: Introductionmentioning

confidence: 99%

Amine–Borane Dehydropolymerization: Challenges and Opportunities

Colebatch

Weller

2018

Chemistry A European J

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“…In the realm of polymeric materials, − Manners pioneered the substitution of B–N and B–P for C–C units in the backbone of polyolefins, giving rise to exciting new classes of polymeric materials ( A , Figure ). − Expanding on this theme, Helten recently reported the first B–N analogue of polyacetylene ( B ) . We envisioned a strong potential impact of materials in which benzene rings are replaced by azaborinine moieties, given that aromatic groups play a major role in polymer science.…”

Section: Introductionmentioning

confidence: 99%

Changing up BN-Polystyrene: Effect of Substitution Pattern on the Free-Radical Polymerization and Polymer Properties

et al. 2019

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Azaborinine-substituted polymers are poised to dramatically expand the diversity and functionality of polystyrenes via BN for CC substitution, but this new class of materials remains underexplored. Although formally isosteric to the respective all-carbon polystyrene derivatives, polarization due to the difference in electronegativity between B and N can have a distinct effect on polymerizability and the resulting polymer properties. Discussed herein is the successful preparation of a series of new isomeric azaborinine-substituted polymers via standard free-radical polymerization. We investigate the effects of the substitution pattern of vinylated B-mesityl azaborinines, that is, the position of the vinyl group relative to the BN moiety, on the polymerization reactivity and physical properties of the respective polymers. Copolymerization experiments with the parent styrene, as well as meta-and para-mesitylstyrene as direct all-carbon analogues of the azaborinine monomers, reveal that depending on the substitution pattern the more polarized azaborinines are incorporated to a lesser (B-Mes in para-position) or larger extent (B-Mes in meta-position) than the all-carbon analogues. Computational studies offer insights into the subtle electronic effects that result in this differential reactivity. We also compare the polymer properties to those of the all-carbon polystyrene analogues.

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“…BN2VN is a unique vinylborane due to the aromaticity of the 10 π-electron BN naphthalene ring system (Scheme c). The Hückel aromaticity of cyclic conjugated BN materials , is well-established on the basis of resonance stabilization energy, electronic structure, and magnetic properties. − Building on Sneddon’s early work on vinylborazine (VB) polymerization, − several groups have recently explored BN for CC bond substitution in polymer backbones, − conjugated polymers, − or aromatic side chains. ,,, …”

Section: Introductionmentioning

confidence: 99%

An Organoborane Vinyl Monomer with Styrene-like Radical Reactivity: Reactivity Ratios and Role of Aromaticity

et al. 2018

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BN 2-vinylnaphthalene (BN2VN) is a novel precursor to vinyl alcohol copolymers via sodium hydroperoxide oxidation. We show that the unusual aromaticity of the BN heterocycle leads to styrene-like reactivity. Computational data including structural parameters and nucleus independent chemical shift (NICS) values support the aromaticity of the BN naphthalene side chain of BN2VN. Styrene (St) and BN2VN reactivity ratios (r 1 (BN2VN) = 0.423; r 2 (St) = 2.30; r 1 r 2 = 0.97) were determined by nonlinear leastsquares (NLLS) statistical methods. We demonstrate control of copolymer physical properties, including glass transition temperature. This work outlines design principles for the synthesis of tailored polymeric styrene−vinyl alcohol architectures.

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Generation of High‐Molecular‐Weight Polymers with Diverse Substituents: An Unusual Metal‐Free Synthesis of Poly(aminoborane)s

Cited by 9 publications

References 18 publications

Amine–Borane Dehydropolymerization: Challenges and Opportunities

Amine–Borane Dehydropolymerization: Challenges and Opportunities

Changing up BN-Polystyrene: Effect of Substitution Pattern on the Free-Radical Polymerization and Polymer Properties

An Organoborane Vinyl Monomer with Styrene-like Radical Reactivity: Reactivity Ratios and Role of Aromaticity

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