Siloxane Coordination Revisited: Si−O Bond Character, Reactivity and Magnificent Molecular Shapes

Siloxanes have evolved into a multi‐million dollar business due to their manifold of commercial and industrial applications. As siloxanes have high hydrophobicity, low basicity, high flexibility and also high chemical inertness in common, their chemistry differs significantly from that of organic et...

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Veröffentlicht in:	European journal of inorganic chemistry Jg. 2021; H. 29; S. 2907 - 2927
Hauptverfasser:	Dankert, Fabian, Hänisch, Carsten
Format:	Journal Article
Sprache:	Englisch
Veröffentlicht:	Weinheim Wiley Subscription Services, Inc 06.08.2021
Schlagworte:	Basicity Chemical properties Chemistry Coordination Coordination chemistry Crown ethers Host-guest chemistry Hydrophobicity Industrial applications Inorganic chemistry Inorganic macrocycles Macrocycles Silicon Siloxanes Si−O bond activation Templates
ISSN:	1434-1948, 1099-0682
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Abstract	Siloxanes have evolved into a multi‐million dollar business due to their manifold of commercial and industrial applications. As siloxanes have high hydrophobicity, low basicity, high flexibility and also high chemical inertness in common, their chemistry differs significantly from that of organic ethers. The discovery of organic crown ethers, for instance, is commonly accepted as the birth of synthetic host‐guest chemistry. Regarding the chemical properties of siloxanes, cyclic siloxanes which formally resemble silicon analogues of crown ethers, have received considerably less interest in terms of their host‐guest chemistry. Hence, only little is known about siloxane coordination chemistry in the chemical community and the number of published works in this field has been very low till lately. In the last few years, the field has significantly advanced and elegant methods were established to enable the Si−O−Si unit for coordination. This review therefore summarizes the recent developments in the field, recapitulates the historical aspects of siloxane coordination chemistry and describes the specific Si−O bond character with regard to different siloxane linkages. Implications on Si−O bond activation are included and the limits of siloxane coordination are redefined. Host guest‐chemistry with a variety of siloxane ligands has been established over the years. This review tackles the recent developments in the field, recapitulates the historical aspects of siloxane coordination chemistry and describes the specific Si−O bond character with respect to different siloxane linkages. Implications on Si−O bond activation are included, and the limits of siloxane coordination are redefined.
AbstractList	Siloxanes have evolved into a multi‐million dollar business due to their manifold of commercial and industrial applications. As siloxanes have high hydrophobicity, low basicity, high flexibility and also high chemical inertness in common, their chemistry differs significantly from that of organic ethers. The discovery of organic crown ethers, for instance, is commonly accepted as the birth of synthetic host‐guest chemistry. Regarding the chemical properties of siloxanes, cyclic siloxanes which formally resemble silicon analogues of crown ethers, have received considerably less interest in terms of their host‐guest chemistry. Hence, only little is known about siloxane coordination chemistry in the chemical community and the number of published works in this field has been very low till lately. In the last few years, the field has significantly advanced and elegant methods were established to enable the Si−O−Si unit for coordination. This review therefore summarizes the recent developments in the field, recapitulates the historical aspects of siloxane coordination chemistry and describes the specific Si−O bond character with regard to different siloxane linkages. Implications on Si−O bond activation are included and the limits of siloxane coordination are redefined. Host guest‐chemistry with a variety of siloxane ligands has been established over the years. This review tackles the recent developments in the field, recapitulates the historical aspects of siloxane coordination chemistry and describes the specific Si−O bond character with respect to different siloxane linkages. Implications on Si−O bond activation are included, and the limits of siloxane coordination are redefined. Siloxanes have evolved into a multi‐million dollar business due to their manifold of commercial and industrial applications. As siloxanes have high hydrophobicity, low basicity, high flexibility and also high chemical inertness in common, their chemistry differs significantly from that of organic ethers. The discovery of organic crown ethers, for instance, is commonly accepted as the birth of synthetic host‐guest chemistry. Regarding the chemical properties of siloxanes, cyclic siloxanes which formally resemble silicon analogues of crown ethers, have received considerably less interest in terms of their host‐guest chemistry. Hence, only little is known about siloxane coordination chemistry in the chemical community and the number of published works in this field has been very low till lately. In the last few years, the field has significantly advanced and elegant methods were established to enable the Si−O−Si unit for coordination. This review therefore summarizes the recent developments in the field, recapitulates the historical aspects of siloxane coordination chemistry and describes the specific Si−O bond character with regard to different siloxane linkages. Implications on Si−O bond activation are included and the limits of siloxane coordination are redefined.
Author	Hänisch, Carsten Dankert, Fabian
Author_xml	– sequence: 1 givenname: Fabian surname: Dankert fullname: Dankert, Fabian email: fabian.dankert@catalysis.de organization: e. V. (LIKAT Rostock) – sequence: 2 givenname: Carsten surname: Hänisch fullname: Hänisch, Carsten email: carsten.vonhaenisch@staff.uni-marburg.de organization: Philipps-Universität Marburg
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Notes	Dedicated to Prof. Robert “Bob” West for his ground‐breaking research in silicon chemistry. ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14
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Snippet	Siloxanes have evolved into a multi‐million dollar business due to their manifold of commercial and industrial applications. As siloxanes have high...
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SubjectTerms	Basicity Chemical properties Chemistry Coordination Coordination chemistry Crown ethers Host-guest chemistry Hydrophobicity Industrial applications Inorganic chemistry Inorganic macrocycles Macrocycles Silicon Siloxanes Si−O bond activation Templates
Title	Siloxane Coordination Revisited: Si−O Bond Character, Reactivity and Magnificent Molecular Shapes
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