Highly Efficient Synthesis of Boron‐ and Germanium‐Substituted Unsymmetrical Disilazanes

Kaźmierczak, Joanna; Kuciński, Krzysztof; Szudkowska-Frątczak, Justyna; Hreczycho, Grzegorz

doi:10.1002/ejic.201700083

Cited by 10 publications

(5 citation statements)

References 27 publications

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“…Hydrosilylation of unsaturated organoborane compounds bearing functional groups such as vinyl, allyl and acetylene has been reported in many publications [34–36] . In our previous research, we studied the reactions of obtaining silsesquioxane derivatives from unsaturated boranes in a form of vinyl‐ and allylboronates by hydrosilylation with Si−H moiety‐bearing mono‐ and octaspherosilicates catalyzed by Karstedt's catalyst.…”

Section: Introductionmentioning

confidence: 99%

“…[15] Hydrosilylation of unsaturated organoborane compounds bearing functional groups such as vinyl, allyl and acetylene has been reported in many publications. [34][35][36] In our previous research, we studied the reactions of obtaining silsesquioxane derivatives from unsaturated boranes in a form of vinyl-and allylboronates by hydrosilylation with SiÀ H moiety-bearing mono-and octaspherosilicates catalyzed by Karstedt's catalyst. High conversion of substrates prompted us to obtain new borasilsesquioxane derivatives in a hydrosilylation reaction with commercially available compounds containing SiÀ H groups by a reverse approach.…”

Section: Introductionmentioning

confidence: 99%

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Silane‐Bearing Borasilsesquioxanes: Synthetic Protocol and Unsuspected Redistribution Reactions

et al. 2023

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The presented work is a continuation of research on the reactivity of unsaturated borasilsesquioxanes under the conditions of common organometallic transformations. The catalytic hydrosilylation reaction with silanes, siloxanes and silsesquioxanes in presence of platinum catalyst was explored. The majority of the products were obtained in high yields (> 90 %) and their structures were confirmed and characterized by spectroscopy and spectrometry, i. e. NMR and MALDI-TOF-MS.The most significant segment of the work is research on the spontaneous redistribution reaction of the alkoxy group from silane to borane moiety occurring in the obtained products, not being limited to the heterosilsesquioxane chemistry, however. The products were confirmed using GC-MS, ESI-MS methods and B3LYP exchange-correlation, in order to ascertain formation of the silicon-boron hybrid molecule.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Silane‐Bearing Borasilsesquioxanes: Synthetic Protocol and Unsuspected Redistribution Reactions

et al. 2023

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“…[15] A large number of studies have shown that the ultimate properties of ceramic materials are closely related to the elemental components that they contain. [16,17] For example, the SiC binary ceramic system exhibits β-SiC crystallization at 1000 °C, and when it reaches 1200 °C, the material can no longer maintain its ceramic properties. [18,19] When N is introduced to form a ternary ceramic system, the crystallization temperature can rise to 1400 °C.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on the Mechanism of the Initial Ammonolysis Reactions of the Main Raw Materials for the Formation of SiBCN Ceramics

et al. 2021

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A detailed mechanism investigation of the formation of B−N, Si−N and C−N bonds is conducive to the design and synthesis of siliconboroncarbonitride (SiBCN) ceramics to meet application requirements under extreme conditions. Boron trichloride (BCl3), methyldichlorosilane (MDCS) and methylvinyldichlorosilane (MVCS) are the most commonly used raw materials, and they can react with amino compounds, such as ammonia (NH3), methyl ammonium (CH3NH2), and hexamethyldisilazane (HMDZ, (CH3)6Si2NH) in the synthesis of SiBCN precursors. In this paper, quantum chemical calculations were used to study the ammonolysis mechanism of three raw materials with three amino compounds at the M06‐2X/6‐311G(d,p) level of theory. The structural properties, reaction pathways, energy barriers, reaction rates, and other aspects were discussed in detail. The results show that compounds containing B−N, Si−N and C−N bonds can be formed through a synergistic reaction mechanism with the release of ammonium chloride or trimethylchlorosilane (TMCS). The ammonolysis processes of BCl3 have absolute advantages in both kinetics and thermodynamics. The reaction of MDCS has the lowest energy barrier. All ammonolysis reactions are thermodynamically exothermic processes. The calculated results agree well with the experimental observations and provide an explanation for the initiation process of precursor synthesis.

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“…Traditionally, conventional methods using halo‐compounds are used to modify their structure, however catalytic solutions are becoming increasingly investigated . On the other hand, the boron modification of various compounds, polymers, and nanoparticles is attractive for a wide range of applications . Si‐ O ‐B moiety, which is a core of poly(borasiloxane)s, is very interesting in terms of modern polymer chemistry .…”

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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Highly Efficient Synthesis of Boron‐ and Germanium‐Substituted Unsymmetrical Disilazanes

Cited by 10 publications

References 27 publications

Silane‐Bearing Borasilsesquioxanes: Synthetic Protocol and Unsuspected Redistribution Reactions

Silane‐Bearing Borasilsesquioxanes: Synthetic Protocol and Unsuspected Redistribution Reactions

Theoretical Study on the Mechanism of the Initial Ammonolysis Reactions of the Main Raw Materials for the Formation of SiBCN Ceramics

Introduction of Boron Functionalities into Silsesquioxanes: Novel Independent Methodologies

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