Tetra-functional double-decker silsesquioxanes as anchors for reactive functional groups and potential synthons for hybrid materials

Mituła, Katarzyna; Duszczak, Julia; Brząkalski, Dariusz; Dudziec, Beata; Kubicki, Maciej; Marciniec, Bogdan

doi:10.1039/c7cc03958a

Cited by 19 publications

(21 citation statements)

References 25 publications

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“…At the same time, chemists are looking for synthetic routes exploiting among others hydrosilylation reaction to obtain novel, functionalized Si-based reagents with a specific structure such as silsesquioxanes. [17][18][19][20][21][22][23][24][25][26][27] While hydrosilylation of olefins with silanes has been widely studied, [3,28] the reports on T 8 silsesquioxanes are limited [5,6,[29][30][31][32][33][34] and for double-decker systems of both closed (D 2 T 8 [4,19,25,[35][36][37] ) and opened (M 4 T 8 [38][39][40][41][42][43] ) structure even more scant. [5] Cage-like derivatives have driven much attention due to specific physicochemical properties (governed by the nature of their silicate rigid core and by the number and type of functional groups attached to it) affecting directions of their broad applications from material chemistry to medicine.…”

Section: Introductionmentioning

confidence: 99%

“…[6][7][8][9][10][11] Nowadays, scientists are mostly focused on the investigation of possible modifications and further use of cubic T 8 cages and, for the last decade, doubledecker silsesquioxane (DDSQ) systems too. [42] The reported studies basically were focused on the synthesis and further application of properly tetrasubstituted DDSQ-based silsesquioxanes. [5,12] The double-decker silsesquioxane structure differs from the symmetric, cubic one and features opened (M 4 T 8 = DDSQ-4OSi [13] ) or closed (D 2 T 8 = DDSQ-2Si [14] ) frameworks with either two or four reactive moieties.…”

Section: Introductionmentioning

confidence: 99%

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Highly Efficient Route for the Synthesis of a Novel Generation of Tetraorganofunctional Double‐decker Type of Silsesquioxanes

et al. 2019

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We present an efficient methodology for the synthesis of tetrafunctionalized double-decker silsesquioxanes via hydrosilylation reaction. An investigation of the catalytic system, olefin structure, chemical and steric surrounding of SiÀ H moiety in the respective reagent was carried out on the progress, selectivity and rate of hydrosilylation process. Two alternative synthetic pathways for obtaining a variety of functionalized double-decker silsesquioxanes with high yields based on the Pt catalysts were developed. These parallel routes concern reverse SiÀ H and À CH=CH 2 reactive groups placement in the doubledecker silsesquioxane core. As a result, a series of new tetrasubstituted double-decker silsesquioxanes derivatives were obtained with high yield and selectivity and comprehensively characterized in detail by spectroscopic analyses.[a] J.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Highly Efficient Route for the Synthesis of a Novel Generation of Tetraorganofunctional Double‐decker Type of Silsesquioxanes

et al. 2019

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“…[9][10][11][12] Recently,t he synthesis of functionalizeds ilsesquioxanes cages( SQs) containing other heteroatomsa nd functional groupsh as been strongly developed by many scientists. [23][24][25][26][27][28] On the other hand, the boron modification of variousc ompounds, [29][30][31][32][33] polymers, [34,35] and nanoparticles is attractivef or aw ide range of applications. [23][24][25][26][27][28] On the other hand, the boron modification of variousc ompounds, [29][30][31][32][33] polymers, [34,35] and nanoparticles is attractivef or aw ide range of applications.…”

Section: Introductionmentioning

confidence: 99%

Introduction of Boron Functionalities into Silsesquioxanes: Novel Independent Methodologies

Kaźmierczak

Kuciński

Stachowiak

et al. 2018

Chemistry A European J

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Owing to their versatile application possibilities, silsesquioxanes (SQs) are of considerable interest for creating hybrid inorganic-organic materials. In this report, two novel and independent strategies for the direct attachment of boron functionalities to silsesquioxanes are presented. Encouraged by our previous work concerning the synthesis of borasiloxanes through the catalyst-free dehydrogenative coupling of silanols and boranes, we decided to apply our method to a synthesis of various boron-functionalized silsesquioxanes. During our tests, we also investigated the activity of scandium(III) triflate, which we have previously used as an excellent catalyst for the obtaining of Si-O-Si and Si-O-Ge moieties. As a result, we also discovered a novel approach for the O-borylation of Si-OH groups in silsesquioxanes with allylborane. Both routes are highly chemoselective and efficiently lead to the obtaining of Si-O-B moiety under air atmosphere and at room temperature.

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“…The product, i.e., tetra(hydrodimethylsilyl)-substituted double-decker silsesquioxane, was used for hydrosilylation with 1,9-decadiene. The final product was obtained with the yield of 93% [25]. …”

Section: Experimental Section For the Synthesis Of Trialkenyl-and Tetmentioning

confidence: 99%

“…The obtained products made precursors for hydrosilylation. The procedures were based on the general methodology for alkenyl-substituted silsesquioxanes [24][25][26]. The compounds were synthesized in the Centre for Advanced Technologies, AMU (Poznań, Poland).…”

Section: Experimental Section For the Synthesis Of Trialkenyl-and Tetmentioning

confidence: 99%

Multi-Alkenylsilsesquioxanes as Comonomers and Active Species Modifiers of Metallocene Catalyst in Copolymerization with Ethylene

et al. 2018

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Abstract:The copolymers of ethylene (E) with open-caged iso-butyl-substituted tri-alkenyl-silsesquioxanes (POSS-6-3 and POSS-10-3) and phenyl-substituted tetra-alkenyl-silsesquioxane (POSS-10-4) were synthesized by copolymerization over the ansa-metallocene catalyst. The influence of the kind of silsesquioxane and of the copolymerization conditions on the reaction performance and on the properties of the copolymers was studied. In the case of copolymerization of E/POSS-6-3, the positive comonomer effect was observed, which was associated with the influence of POSS-6-3 on transformation of the bimetallic ion pair to the active catalytic species. Functionality of silsesquioxanes and polymerization parameters affected the polyhedral oligomeric silsesquioxanes (POSS) contents in the copolymers which varied in the range of 1.33-7.43 wt %. Tri-alkenyl-silsesquioxanes were incorporated into the polymer chain as pendant groups while the tetra-alkenyl-silsesquioxane derivative could act as a cross-linking agent which was proved by the changes in the contents of unsaturated end groups, by the glass transition temperature values, and by the gel contents (up to 81.3% for E/POSS-10-4). Incorporation of multi-alkenyl-POSS into the polymer chain affected also the melting and crystallization behaviors.

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Tetra-functional double-decker silsesquioxanes as anchors for reactive functional groups and potential synthons for hybrid materials

Cited by 19 publications

References 25 publications

Highly Efficient Route for the Synthesis of a Novel Generation of Tetraorganofunctional Double‐decker Type of Silsesquioxanes

Highly Efficient Route for the Synthesis of a Novel Generation of Tetraorganofunctional Double‐decker Type of Silsesquioxanes

Introduction of Boron Functionalities into Silsesquioxanes: Novel Independent Methodologies

Multi-Alkenylsilsesquioxanes as Comonomers and Active Species Modifiers of Metallocene Catalyst in Copolymerization with Ethylene

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