Synthesis of Structurally Precise Polysiloxanes via the Piers–Rubinsztajn Reaction

Chen, Xunjun; Yi, Minghao; Wu, Shufang; Tan, Lewen; Ge, Xin; He, Ming; Yin, Geping

doi:10.3390/ma12020304

Cited by 11 publications

(5 citation statements)

References 62 publications

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“…Piers–Rubinsztajn (PR) chemistry is one method to be considered. We have previously demonstrated the use of PR chemistry in coupling triarylamines to siloxane oligomers or polymers for the generation of new materials. − This type of chemistry has also been used to make many other functional materials such as siloxane-based foams, , surfactants, cross-linkers with lignin, elastomers, , polymers, − dendrons, , and other unique cyclic macrocycles . The PR reaction uses tris(pentafluorophenyl)borane as an organic Lewis acid catalyst, coupling a Si–H bond to an oxygen-based nucleophile and then forming a Si–O bond. − Examples of oxygen-based nucleophiles include hydroxy (−OH) and ether (−OR) groups and yield hydrogen (H 2 ) or methane (CH 4 ) as a byproduct.…”

Section: Introductionmentioning

confidence: 99%

Use of Piers–Rubinsztajn Chemistry to Access Unique and Challenging Silicon Phthalocyanines

et al. 2021

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Axial functionalization is one mode that enables the solubility of silicon phthalocyanines (SiPcs). Our group observed that the use of typical axial functionalization methodologies on reaction of Cl2SiPc with the chlorotriphenyl silane reagent unexpectedly resulted in the equal formation of triphenyl silyloxy silicon tetrabenzotriazacorrole ((3PS)-SiTbc) and the desired bis(tri-phenyl siloxy)-silicon phthalocyanine ((3PS)2-SiPc). The formation of a (3PS)-SiTbc was unexpected, and the separation of (3PS)-SiTbc and (3PS)2-SiPc was difficult. Therefore, in this study, we investigated the use of Piers–Rubinsztajn (PR) chemistry as an alternative method to functionalize the axial position of a SiPc to avoid the generation of a Tbc derivative. PR chemistry is a novel method to form a Si–O bond starting with a Si–H-based reactant and a −OH-based nucleophile enabled by tris(pentafluorophenyl)borane as a catalyst. The PR chemistry was screened on several fronts on how it can be applied to SiPcs. It was found that the process needs to be run in nitrobenzene at a molar ratio and at a particular temperature. To this end, the triphenylsiloxy derivative (3PS)2-SiPc was produced and fully characterized, without the production of a Tbc derivative. In addition, we explored and outlined that the PR chemistry method can enable the formation of other SiPc derivatives that are inaccessible utilizing other established axial substitution chemistry methods such as (TM3)2-SiPc and (MDM)2-SiPc. These additional materials were also physically characterized. The main conclusion is that the PR chemistry method can be applied to SiPcs and yield several alternative derivatives and has the potential to apply to additional macrocyclic compounds for unique derivative formation.

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Section: Introductionmentioning

confidence: 99%

Use of Piers–Rubinsztajn Chemistry to Access Unique and Challenging Silicon Phthalocyanines

et al. 2021

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“…In particular, developing Si-HBPs via simple, rapid and mild synthetic procedures is highly desirable. The Piers-Rubinsztajn (P-R) reaction, namely the condensation of alkoxysilanes with hydrosilanes, has rapidly developed since it was found in the 1990s [22,23], because this strategy is mild and provides a possibility for the controlled or precise synthesis of silicones, including small molecules, linear polymers, and crosslinked materials [24][25][26][27][28][29][30][31]. For example, the P-R coupling reactions of various organic tris(dimethylsiloxy)silane and trialkoxysilane compounds can generate a series of cyclic polysiloxanes with cyclotetrasiloxane subunits in a simple one-step synthesis [32].…”

Section: Introductionmentioning

confidence: 99%

Hyperbranched Polycarbosiloxanes: Synthesis by Piers-Rubinsztajn Reaction and Application as Precursors to Magnetoceramics

Zhang

Xue

et al. 2020

Polymers

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Silicon-containing hyperbranched polymers (Si-HBPs) have drawn much attention due to their promising applications. However, the construction of Si-HBPs, especially those containing functional aromatic units in the branched backbones by the simple and efficient Piers-Rubinsztajn (P-R) reaction, has been rarely developed. Herein, a series of novel hyperbranched polycarbosiloxanes were prepared by the P-R reactions of methyl-, or phenyl-triethoxylsilane and three Si-H containing aromatic monomers, including 1,4-bis(dimethylsilyl)benzene, 4,4 -bis(dimethylsilyl)-1,1 -biphenyl and 1,1 -bis(dimethylsilyl)ferrocene, using B(C 6 F 5 ) 3 as the catalyst for 0.5 h at room temperature. Their structures were fully characterized by Fourier transform infrared spectroscopy, 1 H NMR, 13 C NMR, and 29 Si NMR. The molecular weights were determined by gel permeation chromatography. The degrees of branching of these polymers were 0.69-0.89, which were calculated based on the quantitative 29 Si NMR spectroscopy. For applications, the ferrocene-linked Si-HBP can be used as precursors to produce functional ceramics with good magnetizability after pyrolysis at elevated temperature.

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“…This process was named the Pierce–Rubinsztajn (P-R) reaction [ 23 ] and found numerous applications in the synthesis of siloxane polymers. See recent papers [ 24 , 25 , 26 , 27 ]. The P-R reaction allows the synthesis of many siloxanes and silyl ether polymers and their copolymers.…”

Section: Introductionmentioning

confidence: 99%

Tris(pentafluorophenyl)borane-catalyzed Hydride Transfer Reactions in Polysiloxane Chemistry—Piers–Rubinsztajn Reaction and Related Processes

2023

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Tris(pentafluorophenyl)borane (TPFPB) is a unique Lewis acid that catalyzes the condensation between hydrosilanes (Si-H) and alkoxysilanes (Si-OR), leading to the formation of siloxane bonds (Si-OSi) with the release of hydrocarbon (R-H) as a byproduct—the so-called Piers–Rubinsztajn reaction. The analogous reactions of hydrosilanes with silanols (Si-OH), alcohols (R-OH), ethers (R-OR′) or water in the presence of TPFPB leads to the formation of a siloxane bond, alkoxysilane (Si-OR or Si-OR′) or silanol (Si-OH), respectively. The above processes, often referred to as Piers–Rubinsztajn reactions, provide new synthetic tools for the controlled synthesis of siloxane materials under mild conditions with high yields. The common feature of these reactions is the TPFPB-mediated hydride transfer from silicon to carbon or hydrogen. This review presents a summary of 20 years of research efforts related to this field, with a focus on new synthetic methodologies leading to numerous previously difficult to synthesize well-defined siloxane oligomers, polymers and copolymers of a complex structure and potential applications of these new materials. In addition, the mechanistic aspects of the recently discovered reactions involving hydride transfer from silicon to silicon are discussed in more detail.

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Synthesis of Structurally Precise Polysiloxanes via the Piers–Rubinsztajn Reaction

Cited by 11 publications

References 62 publications

Use of Piers–Rubinsztajn Chemistry to Access Unique and Challenging Silicon Phthalocyanines

Use of Piers–Rubinsztajn Chemistry to Access Unique and Challenging Silicon Phthalocyanines

Hyperbranched Polycarbosiloxanes: Synthesis by Piers-Rubinsztajn Reaction and Application as Precursors to Magnetoceramics

Tris(pentafluorophenyl)borane-catalyzed Hydride Transfer Reactions in Polysiloxane Chemistry—Piers–Rubinsztajn Reaction and Related Processes

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