Synthesis of Chlorosilicates

Steinhauer, Simon; Böttcher, Tobias; Schwarze, Nico; Neumann, Beate; Stammler, Hans‐Georg; Hoge, Berthold

doi:10.1002/anie.201406311

Cited by 31 publications

(35 citation statements)

References 29 publications

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“…Utilizing methyl-, ethyl-, n-butyl-, phenyl-, p-tolyl-, diethylamino-and phenoxy-element chlorides ac onsiderable number of compounds featuring one, two or three pentafluoroethyl groups are accessible (Scheme3 and Ta ble 1). [18,[22][23][24][25][26] All new organo(pentafluoroethyl)element compounds exhibit as ufficient thermal stabilitya nd are, apart from the triarylstannanes,isolated as colorless liquidsvia distillation.…”

Section: General Synthesis Of Pentafluoroethyl-element Compoundsmentioning

confidence: 99%

Pentafluoroethylated Compounds of Silicon, Germanium and Tin

Wiesemann

Hoge

2018

Chemistry A European J

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In this contribution we present an account on pentafluoroethylated compounds of silicon, germanium and tin. The pronounced electron-withdrawing effect of the pentafluoroethyl group leads to a markedly increased Lewis acidity at the central atom which results in the stabilization of hypervalent complexes, anionic element(II) species as well as remarkable reactivities of element-element and element-hydrogen bonds. By addition to unsaturated C-C bonds or by reaction with organic halides as well as transition-metal complexes the molecules bearing a pentafluoroethyl-element group are readily accessible. Moreover, the utilization of pentafluoroethyl groups facilitates the formation of donor-stabilized germylenes and stannylenes. A series of such compounds serves as suitable pentafluoroethylation reagents. Conversely to the well-studied trifluoromethyl derivatives these compounds frequently exhibit a higher thermostability, which allows a more convenient handling.

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Section: General Synthesis Of Pentafluoroethyl-element Compoundsmentioning

confidence: 99%

Pentafluoroethylated Compounds of Silicon, Germanium and Tin

Wiesemann

Hoge

2018

Chemistry A European J

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“…These distances are significantly shorter than in the two only known adducts of an acyclicether with neutral silanes (e.g.2.27 in H 3 SiCl-Me 2 O, stable only in the crystalline state at < 100 K), [17] and rather bear resemblance to ether adducts of silylium cations. [21] As inglet at À90.4 ppm in the 29 Si NMR spectrum and X-ray diffraction revealed pentacoordination at silicon. Addition of one equivalent KF/18-crown-6 led to the formation of the fluorosilicate [1-F][K@18-crown-6] (Figure 3a).…”

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confidence: 97%

Bis(perchlorocatecholato)silane—A Neutral Silicon Lewis Super Acid

et al. 2018

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No neutral silicon Lewis super acids are known to date. We report on the synthesis of bis(perchlorocatecholato)silane and verify its Lewis super acidity by computation (DLPNO-CCSD(T)) and experiment (fluoride abstraction from SbF ). The exceptional affinity towards donors is further demonstrated by, for example, the characterization of an unprecedented SiO F dianion and applied in the first hydrodefluorination reaction catalyzed by a neutral silicon Lewis acid. Given the strength and convenient access to this new Lewis acid, versatile applications might be foreseen.

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“…[12] und die anschließende Umsetzung mit HSiCl 3 in CH 3 CN führten zur Ausfällung von 1-(CH 3 CN) 2 unter Freisetzung von HCl und H 2 .E sw urde eine gute Gesamtausbeute (85 %) im > 3g Maßstab erreicht. [19] Das Bisaddukt steht im Gegensatz zu Si(cat F ) 2 und dem nicht-halogenierten Si(cat) 2 ,fürdie nur die Monoanionen beschrieben wurden, [8,20] [21] Ein Singulett bei À90.4 ppm im 29 Si-NMR-Spektrum und Rçntgenbeugung zeigten auf,d ass das Silicium pentagonalkoordiniert vorlag. Die C N-Streckschwingung von 1-(CH 3 CN) 2 (2335 cm À1 ), die im Vergleich zum freien CH 3 CN (2249 cm À1 )u m8 6cm À1 blauverschoben ist, deutet auf eine hohe Lewis-Aziditäth in.…”

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