Synthesis and Coordination of the Cagelike Siloxane Compounds E2{(SiMe2)2O}3 (E = As, Sb, Bi)

Bimbös, Christian; Jost, Maximilian; Hänisch, Carsten von; Harms, Klaus

doi:10.1002/ejic.201300479

Cited by 3 publications

(2 citation statements)

References 33 publications

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“…After conversion of these salts with D 6 in SO 2(l) , the respective coordination compounds [Ag(D 6 )Al F ] ( 11 ) and [Ag(D 6 )FAl(OR F ) 3 ] ( 12 ) were isolated and characterized [53] . Besides the two‐dimensional D n ligands, our group expanded the field to three‐dimensional ligand systems introducing group 15 elements [132–135] . The application of Si−O donors for coordination was unfortunately unsuccessful in the most cases.…”

Section: Siloxane Coordination Compoundsmentioning

confidence: 99%

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

Dankert

Hänisch

2021

Eur J Inorg Chem

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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.

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Section: Siloxane Coordination Compoundsmentioning

confidence: 99%

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

Dankert

Hänisch

2021

Eur J Inorg Chem

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“…For some time we have been interested in the functionalization of dichlorodisiloxanes with phosphorus or arsenic reagents, such as [Li(dme)EH 2 ] (for E = P, As) 5,7–10. In the case of the methyl‐substituted 1,3‐dichloro‐1,1,3,3‐tetramethyldisiloxane (ClSiMe 2 ) 2 O, treatment with [Li(dme)EH 2 ] (for E = P, As) leads to the formation of well‐defined cage structures E 2 [(SiMe 2 ) 2 O] 3 (E = P, As) 5,11. In a heterogeneous reaction, the same dichlorodisiloxane reacts with Na 3 E (for E = Sb, Bi) to afford the equivalent cage compounds E 2 [(SiMe 2 ) 2 O] 3 , so the whole set of heavy group 15 elements as bridgehead atoms for siloxane cage compounds was accessible.…”

Section: Introductionmentioning

confidence: 99%

Corrigendum: Synthesis and Conformational Analysis of Efrapeptins

Weigelt¹,

Huber²,

Hofmann³

et al. 2013

Chemistry A European J

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Stepwise Synthesis of Siloxane‐Substituted Oligoarsanes and Structural Investigation of Alkaline Earth Metal Derivatives

et al. 2015

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The reaction between [Li(dme)AsH2] and (ClSiiPr2)2O gives a mixture of two products: the primary diarsanyldisiloxan (H2AsSiiPr2)2O (5) and the cyclic diarsanylsiloxane (HAsSiiPr2)2O (6). Through metallation of the mixture, the deprotonated species of both compounds could be obtained and isolated. Further reactions between the two metallated cyclic diarsanylsiloxanes (compounds 9 and 10) and (ClSiiPr2)2O both lead to the bicyclic compound As2[(iPr2Si)2O]2 (11). Subsequent oxidative coupling of 9 or 10 with C2H4Br2 as reagent leads to intermolecular As–As bond formation, yielding the quite remarkable compound As6[(iPr2Si)2O]3 (12), which features two siloxane‐bridged As3 rings. Compounds 5–12 were characterized by NMR, elemental analysis and X‐ray crystallography. Quantum chemical calculations were carried out to investigate the formation of the different products when arsenic (compound 12) is substituted by phosphorus (compound 4) in the final oxidation reaction of the cyclic compounds (HESiiPr2)2O. The calculations suggest a reaction path leading to 4 that is in agreement with experimental observations. The theoretical data also provide information that explains the experimental finding that two different products for E = P and E = As are formed under the same oxidative reaction conditions.

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Synthesis and Coordination of the Cagelike Siloxane Compounds E₂{(SiMe₂)₂O}₃ (E = As, Sb, Bi)

Cited by 3 publications

References 33 publications

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

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

Corrigendum: Synthesis and Conformational Analysis of Efrapeptins

Stepwise Synthesis of Siloxane‐Substituted Oligoarsanes and Structural Investigation of Alkaline Earth Metal Derivatives

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