Refernces
10.1080/15421400490478920
The research focuses on the synthesis and characterization of high-performance siloxane-containing polymers. The study employs catalytic cross-dehydrocoupling polymerization of silane and water, and deaminative polymerization between silanol and aminosilane to create silicon-containing polymers with a controlled structure. Key reactants include 1,4-bis(hydroxydimethylsilyl)benzene (BHSB), difunctional silane or siloxane, and n-hexylamine-2-ethylhexoate, which acts as a catalyst for silanol condensation. The research also investigates the use of Pd2(dba)3 as a catalyst and the synthesis of optically active siloxane materials from specific optically active building blocks. Various analyses are used throughout the experiments, including nuclear magnetic resonance (NMR), infrared (IR) spectroscopy, gel permeation chromatography (GPC), vapor pressure osmometry (VPO), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and polarimetry for the determination of molecular weights, chemical structures, thermal properties, and optical activities of the synthesized polymers.
10.1021/acs.organomet.6b00505
The research describes a novel method for the preparation of trihydrosilanes, which are synthetically useful compounds, by merging platinum-catalyzed alkene hydrosilylation with SiH4 surrogates. The purpose of this study was to develop a safer and more efficient alternative to the hazardous handling of monosilane (SiH4), which is flammable and toxic. The researchers used di(cyclohexa-2,5-dien-1-yl)silane as a stable surrogate for SiH4, which, when combined with various α-olefins in the presence of a platinum catalyst, resulted in the formation of monohydrosilylation adducts. These adducts, with cyclohexa-2,5-dien-1-yl substituents acting as protecting groups, were then treated with catalytic amounts of B(C6F5)3 to liberate Si?H bonds and release benzene, yielding trihydrosilanes in a two-step process without the formation of salt waste. The study successfully demonstrated the scalability of this methodology and provided an alternative route for the preparation of trihydrosilanes, avoiding the need to handle gaseous SiH4, AlkylSiCl3, and AlkylSi(OEt)3, while only releasing benzene as waste.
10.1016/00404-0399(50)09172-
The study investigates the cathodic intra- and intermolecular couplings of ketones with unsaturated silanes. The researchers discovered that the electroreduction of 6-trimethylsilyl-6-hepten-2-one resulted in the formation of cis-1-methyl-3-trimethylsilyl cyclohexanol, indicating that the presence of a trimethylsilyl group on the double bond significantly influenced the regioselectivity of the cathodic cyclization, favoring the formation of a 6-membered ring over a 5-membered ring. Additionally, the cathodic intermolecular coupling of ketones with unsaturated silanes yielded γ-trimethylsilyl alcohols. This coupling was found to be highly affected by the substituent on the double bond, with the trimethylsilyl group playing a crucial role in stabilizing intermediate anionic species, thereby promoting the coupling reaction. The study highlights the unique coupling reactions facilitated by the presence of trimethylsilyl groups and their potential applications in organic synthesis.
10.1021/om900444z
The research aimed to develop an alternative and mild route for the generation of N-heterocyclic silylenes, which are of significant interest due to their potential applications in transition metal catalysis. The study focused on the dehydrochlorination of cyclic diaminohydrochlorosilanes using the bulky heterocyclic carbene 1,3-bis(tert-butyl)imidazol-2-ylidene, resulting in the formation of stable and transient four- and five-membered heterocyclic silylenes with various substituents under mild conditions. This approach marked the first non-metallic route for generating heterocyclic silylenes without the need for harsh conditions or highly reactive metallic reagents. Key chemicals used in the process included cyclic diaminochlorosilanes, 1,3-bis(tert-butyl)imidazol-2-ylidene, and a range of amines and silanes, leading to the successful synthesis of various silylenes and providing a new perspective on silylene generation. The conclusions highlighted the effectiveness of this novel route, which allowed for the generation of these silylenes in high yields and with a broad applicability to different substituents on the ligand backbones.
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