Synthesis of Tris‐ and Tetrakis(pentafluoroethyl)silanes

Steinhauer, Simon; Bader, Julia; Stammler, Hans‐Georg; Ignat’ev, Nikolai; Hoge, Berthold

doi:10.1002/anie.201400291

Cited by 49 publications

(33 citation statements)

References 11 publications

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“…[58] Given the redox activity of the electron-rich substituents in combination with the unquenched nature of the now accessible monomeric aminosilanes,apromising potential for ligandelementc ooperativity with this new class of compoundsi so ffered-an objective that is of currenti nteresta nd ongoing research in our group. By variation of the substituents at silicon or at the NNN substituents, the inevitable dimerization, which was recently observed in related species, could be controlled for the first time, yielding either monomeric, structurally reversible, or dimerics pecies.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Electron‐Rich, Planarized Silicon(IV) Species and a Theoretical Analysis of Dimerizing Aminosilanes

Kramer

Jöst

Mackenroth

et al. 2017

Chemistry A European J

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Equipping silicon(IV) with electron-rich, geometrically constrained NNN- and ONO-tridentate substituents leads to aminosilanes with increased Lewis acidity-expressed through the formation of Si N rings by head-to-tail dimerization. Depending on the substituents, the dimerization can be controlled for the first time, yielding monomeric, structurally reversible and dimeric states. The monomeric species display substantial distortions from tetrahedral towards planar geometry at silicon. The dimerization and the Lewis acidity of aminosilanes are rationalized by (conceptual) DFT, NBO, ETS-NOCV and QTAIM methods. The preorganization at silicon, London dispersion between the substituents and resonance phenomena inside the formed Si N tetracycles are identified as driving forces for the dimerization. Comparison with selected aminosilanes permits general conclusions to be reached on the Lewis acidity of silicon species and on the aggregation of amphiphilic compounds.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Electron‐Rich, Planarized Silicon(IV) Species and a Theoretical Analysis of Dimerizing Aminosilanes

Kramer

Jöst

Mackenroth

et al. 2017

Chemistry A European J

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“…The analysis shows an anion with an almost ideal octahedral geometry and trans-oriented pentafluoroethyl groups. The Si À C bond lengths of 198.2(1) pm are significantly longer than those in tetracoordinated pentafluoroethyl substituted silicon compounds [8,[11][12][13][14][15][16] (e.g., (C 2 F 5 ) 2 SiF 2 191.1(1) pm) [8] ). Substitution of the fluorine atoms with pentafluoroethyl groups does not affect the SiÀF distances.…”

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Pentafluoroethylsilicic Acids

et al. 2016

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Pure anhydrous hexafluorosilicic acid (H [SiF ]) is a still elusive species, although its existence in aqueous solutions is well documented. Desiccation inevitably leads to decomposition to form tetrafluorosilane and hydrogen fluoride. An oxonium hexafluorosilicate turned out to not be stable at room temperature. Partial substitution of the fluorine atoms with strong electron-withdrawing perfluoroalkyl groups results in substantial stabilization of the corresponding fluorosilicic acids. Mono- and bis(pentafluoroethyl)-substituted fluorosilicic acids were prepared through conversion of the respective halosilanes (Si(C F ) X , with X=Cl, Br) with aqueous HF, and were obtained as colorless solids. They can be stored at room temperature for several months without decomposition, and thus are the first examples of stable fluorosilicic acids.

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“…[15][16][17][18] In this study, Si(C 2 F 5 ) 3 NEt 2 was obtained in good yields from SiCl 3 NEt 2 and as light excess of LiC 2 F 5 .F urther derivatization of Si(C 2 F 5 ) 3 NEt 2 was achieved through cleavage of the siliconnitrogen bond with HCl or HBr and subsequent halide replacement by ap lethora of nucleophiles,w hich afforded alibrary of tris(pentafluoroethyl)silanes,Si(C 2 F 5 ) 3 X, with X = F, Cl, Br, etc. [15][16][17][18] In this study, Si(C 2 F 5 ) 3 NEt 2 was obtained in good yields from SiCl 3 NEt 2 and as light excess of LiC 2 F 5 .F urther derivatization of Si(C 2 F 5 ) 3 NEt 2 was achieved through cleavage of the siliconnitrogen bond with HCl or HBr and subsequent halide replacement by ap lethora of nucleophiles,w hich afforded alibrary of tris(pentafluoroethyl)silanes,Si(C 2 F 5 ) 3 X, with X = F, Cl, Br, etc.…”

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The Tris(pentafluoroethyl)silanide Anion

et al. 2016

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Tris(pentafluoroethyl)silane, which is conveniently accessible by the treatment of Si(C F ) X (X=Cl, Br) with Bu SnH, was successfully employed for hydrosilylation reactions. In the presence of a palladium catalyst, hydrosilylation of phenylacetylene with Si(C F ) H affords the product of an α-addition whereas the reaction of trimethylsilylacetylene with the silane leads to the β-trans product. Tris(pentafluoroethyl)silane can be deprotonated by sterically demanding bases such as lithium diisopropylamide at low temperatures to give the corresponding silanide ion. The addition of crown ethers or cryptands to this highly reactive species enabled the isolation and characterization of salt-like tris(pentafluoroethyl)silanide at room temperature.

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Synthesis of Tris‐ and Tetrakis(pentafluoroethyl)silanes

Cited by 49 publications

References 11 publications

Synthesis of Electron‐Rich, Planarized Silicon(IV) Species and a Theoretical Analysis of Dimerizing Aminosilanes

Synthesis of Electron‐Rich, Planarized Silicon(IV) Species and a Theoretical Analysis of Dimerizing Aminosilanes

Pentafluoroethylsilicic Acids

The Tris(pentafluoroethyl)silanide Anion

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