Synthesis of 6-, 7- and 8-membered cyclosiloxanes having multifunctional groups

Cho, Hyeon Mo; Lee, Ji Eun; Lee, Myong Euy; Lee, Kang Mun

doi:10.1016/j.jorganchem.2011.04.025

Cited by 4 publications

(2 citation statements)

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“…The presence of N→Si coordination in Ar NCN PhSiH 2 increased the reactivity of the Si−H bonds toward water. The resulting monomeric silanediols are good starting synthons for the synthesis of N ‐coordinated cyclic siloxanes (R 2 SiO) n (Scheme ), that have great importance as precursors to high M w siloxane polymers widely used in industry…”

Section: Group 14 Complexesmentioning

confidence: 99%

(N),C,N‐Coordinated Heavier Group 13–15 Compounds: Synthesis, Structure and Applications

et al. 2020

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The aim of this review is to summarize recent achievements in the field of (N),C,N‐coordinated group 13–15 compounds not only regarding their synthesis and structure, but mainly focusing on their potential applications. Relevant compounds contain various types of N‐coordinating ligands built up on an ortho‐(di)substituted phenyl platform. Thus, group 13 and 14 derivatives were used as single‐source precursors for the deposition of semiconducting thin films, as building blocks for the preparation of high‐molecular polymers with remarkable optical and chemical properties or as compounds with interesting reactivity in hydrometallation processes. Group 15 derivatives function as catalysts in the Mannich reaction, in the allylation of aldehydes or activation of CO2. They were used as transmetallation reagents in transition metal catalysed coupling reactions. The univalent species serve as ligands for transition metals, activate alkynes or alkenes and are utilized as catalysts in the transfer hydrogenation of azo‐compounds.

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Section: Group 14 Complexesmentioning

confidence: 99%

(N),C,N‐Coordinated Heavier Group 13–15 Compounds: Synthesis, Structure and Applications

et al. 2020

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“…Given the extensive applications of silicones as functional materials, the synthesis of siloxanes directly from readily available compounds without producing chemical waste is very important. , Such a synthesis of siloxanes with predictable size and selectivity by conventional methods is difficult, and potential synthetic methods remain to be explored . For example, cyclosiloxanes are building blocks of various silicon-based polymeric materials. , However, the conventional synthesis of cyclosiloxanes involves hydrolysis of chlorosilane and alkoxysilane and self-condensation of siloxane diols and siloxane polyols. ,, In general, these reactions require high temperature and excess amounts of base and lead to the formation of a number of side products such as silanols, cyclosiloxanes, and oligo- and polysiloxanes …”

Section: Introductionmentioning

confidence: 99%

Cobalt-Catalyzed Selective Synthesis of Disiloxanes and Hydrodisiloxanes

Pattanaik

Gunanathan

2019

ACS Catal.

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Selective syntheses of symmetrical siloxanes and cyclotetrasiloxanes are attained from reactions of silanes and dihydrosilanes, respectively, with water, and the reactions are catalyzed by a NNNHtBu cobalt(II) pincer complex. Interestingly, when phenylsilane was subjected to catalysis with water, a siloxane cage consisting 12 silicon and 18 oxygen centers was obtained and remarkably the reaction proceeded with liberation of 3 equiv of molecular hydrogen (36 H2) under mild experimental conditions. Upon reaction of silane with different silanols, highly selective and controlled syntheses of higher order monohydrosiloxanes and disiloxymonohydrosilanes were achieved by cobalt catalysis. The liberated molecular hydrogen is the only byproduct observed in all of these transformations. Mechanistic studies indicated that the reactions occur via a homogeneous pathway. Kinetic and independent experiments confirmed the catalytic oxidation of silane to silanol, and further dehydrocoupling processes are involved in syntheses of symmetrical siloxanes, cyclotetrasiloxanes, and siloxane cage compounds, whereas the unsymmetrical monohydrosiloxane syntheses from silanes and silanols proceeded via dehydrogenative coupling reactions. Overall these cobalt-catalyzed oxidative coupling reactions are based on the Si–H, Si–OH, and O–H bond activation of silane, silanol, and water, respectively. Catalytic cycles consisting of Co(II) intermediates are suggested to be operative.

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