Approaches to polymers containing a silicon-oxygen bond in the main chain

Kawakami, Yusuke; Li, Yuning

doi:10.1163/156855500750206357

Cited by 21 publications

(13 citation statements)

References 79 publications

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“…Complex 1 also efficiently catalyzes the reaction of silanes with alcohols as an inter molecular variant of the release of “krypto”‐hydrogen 30. We are especially interested in the dehydrogenative alcoholysis of silanes with diols to yield oligo‐ or poly(alkyl silyl ethers) which has been scarcely exploited to date 31–33. The use of iron‐based catalysts for this type of reaction is unprecedented.…”

Section: Methodsmentioning

confidence: 99%

Low‐Valent Iron(I) Amido Olefin Complexes as Promotors for Dehydrogenation Reactions

et al. 2015

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Fe(I) compounds including hydrogenases show remarkable properties and reactivities. Several iron(I) complexes have been established in stoichiometric reactions as model compounds for N2 or CO2 activation. The development of well-defined iron(I) complexes for catalytic transformations remains a challenge. The few examples include cross-coupling reactions, hydrogenations of terminal olefins, and azide functionalizations. Here the syntheses and properties of bimetallic complexes [MFe(I) (trop2 dae)(solv)] (M=Na, solv=3 thf; M=Li, solv=2 Et2 O; trop=5H-dibenzo[a,d]cyclo-hepten-5-yl, dae=(N-CH2 -CH2 -N) with a d(7) Fe low-spin valence-electron configuration are reported. Both compounds promote the dehydrogenation of N,N-dimethylaminoborane, and the former is a precatalyst for the dehydrogenative alcoholysis of silanes. No indications for heterogeneous catalyses were found. High activities and complete conversions were observed particularly with [NaFe(I) (trop2 dae)(thf)3 ].

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Section: Methodsmentioning

confidence: 99%

Low‐Valent Iron(I) Amido Olefin Complexes as Promotors for Dehydrogenation Reactions

et al. 2015

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“…Wir sind vor allem interessiert an der dehydrierenden Alkoholyse von Silanen mit Diolen. Dieser mögliche Zugang zu Oligo‐ oder Poly(alkylsilylethern) wurde bislang kaum genutzt 31–33. Die Verwendung von eisenbasierten Katalysatoren für diese Reaktion ist beispiellos.…”

Section: Methodsunclassified

Niedervalente Eisen(I)‐Amido‐Olefinkomplexe als Promotoren von Dehydrierungsreaktionen

et al. 2015

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Fe I -Verbindungen einschließlichH ydrogenasen [1a] zeigen bemerkenswerte Stoffeigenschaften und Reaktivitäten. [2][3][4][5][6] Das Anion [Fe(C(SiMe 3 ) 3 ) 2 ] À ist ein Einzelmolekülmagnet mit hoher Anisotropiebarriere. [2a] In stçchiometrischen Reaktionen wurden Eisen(I)-Diketiminate,E isen(I)-Tris(phosphino)borate und verwandte Spezies als Modellverbindungen für die N 2 -Aktivierung [4a-c,l, 5a,f] sowied ie Spaltung und Kupplung von CO 2 etabliert. [4d,e] Die Entwicklung wohldefinierter Eisen(I)-Komplexef ür katalytischeU msetzungen bleibt jedoche ine Herausforderung. Die wenigen Beispiele umfassen Kreuzkupplungen, [2b,3] Hydrierungen terminaler Olefine [4f] und Azidfunktionalisierungen. [4h, 5i] Hier berichten wir über die Herstellung und Eigenschaften bimetallischer Komplexe[ MFe I (trop 2 dae)(solv)] mit einer d 7 -Fe-low-spin-Valenzelektronenkonfiguration (M = Na, solv = 3thf (1); M= Li, solv = 2Et 2 O( 2 ); trop = 5H-Dibenzo[a,d]cyclo-hepten-5yl, dae = (N-CH 2 -CH 2 -N)). Verbindungen 1 und 2 induzieren die Dehydrierung von N,N-Dimethylaminboran, und 1 ist ein Präkatalysator für die dehydrierende Alkoholyse von Silanen. Es wurden keine Hinweise auf heterogene Katalyse gefunden. Vora llem mit [NaFe I (trop 2 dae)(thf) 3 ]( 1 )w urden hohe Aktivitäten und vollständige Umsätze erzielt. Schema 1. Synthese der Komplexe 1 und 2 ausgehend von [FeCl 2 -(thf) n ]; 1: n=1.5; 2: n = 0.

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“…Silicone polymers are a class of organosilicon polymers with repeating Si-O bonds as the main chain and organic groups directly attached to the silicon atoms [ 27 ]. The Si-O bond on the main chain is highly stable [ 28 ], while the organic groups in the side groups provide good compatibility of the Silicone polymers with organic polymers [ 29 , 30 ]. The silicone polymers with multi-amino show good dispersion and excellent compatibility with polyimides in polar solvents [ 31 ].…”

Section: Introductionmentioning

confidence: 99%

Mechanically Strong and Tailorable Polyimide Aerogels Prepared with Novel Silicone Polymer Crosslinkers

Zhang

Deng

Lun

et al. 2022

Gels

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Polyimide (PI) aerogels were prepared using self-designed silicone polymer cross-linkers with multi-amino from low-cost silane coupling agents to replace conventional small-molecule cross-linkers. The long-chain structure of silicone polymers provides more crosslinking points than small-molecule cross-linkers, thus improving the mechanical properties of polyimide. To investigate the effects of amino content and degree of polymerization on the properties of silicone polymers, the different silicone polymers and their cross-linked PI aerogels were prepared. The obtained PI aerogels exhibit densities as low as 0.106 g/cm3 and specific surface areas as high as 314 m2/g, and the maximum Young’s modulus of aerogel is up to 20.9 MPa when using (T-20) as cross-linkers. The cross-linkers were an alternative to expensive small molecule cross-linkers, which can improve the mechanical properties and reduce the cost of PI aerogels.

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Approaches to polymers containing a silicon-oxygen bond in the main chain

Abstract: Preparative methods of polymers containing a silicon-oxygen bond in the main-chain are systematically summarized with emphasis on recent developments in the synthesis of polycarbosiloxanes, poly(silyl ether)s, and poly(silyl ester)s.

Cited by 21 publications

References 79 publications

Low‐Valent Iron(I) Amido Olefin Complexes as Promotors for Dehydrogenation Reactions

Low‐Valent Iron(I) Amido Olefin Complexes as Promotors for Dehydrogenation Reactions

Niedervalente Eisen(I)‐Amido‐Olefinkomplexe als Promotoren von Dehydrierungsreaktionen

Mechanically Strong and Tailorable Polyimide Aerogels Prepared with Novel Silicone Polymer Crosslinkers

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