New Zwitterionic Spirocyclic λ5Si-Silicates with Two Ethane-1,2-diolato(2-), Oxalato(2-), or Benzene-1,2-diolato(2-) Ligands - Synthesis, Structure, and Dynamic Behavior

Reaction of tetramethoxysilane with three molar equivalents of oxalic acid and two molar equivalents of 1-(2-hydroxyethyl)-pyrrolidine or 1-(2-hydroxyethyl)piperidine in tetrahydrofuran yielded the λ 6 Si-silicates 1-(2-hydroxyethyl)pyrrolidinium tris[oxalato(2Ϫ)]silicate (4) and 1-(2-hydroxyethyl)piperidinium tris[oxalato(2Ϫ)]silicate (5). The related germanium compounds 1-(2-hydroxyethyl)piperidinium tris[oxalato(2Ϫ)]germanate (6) and triethylammonium tris[oxalato(2Ϫ)]germanate (7) were synthesized analogously, starting from tetramethoxygermane and using three molar equivalents of oxalic acid and two molar equivalents of 1-(2-hydroxyethyl)piperidine or triethylamine. Compounds 4Ϫ7 Dianionische Tris[oxalato(2؊)]silicat-und Tris[oxalato(2؊)]germanat-Komplexe: Synthese, Eigenschaften und strukturelle Charakterisierung im Festkörper und in LösungInhaltsübersicht. Die Umsetzung von Tetramethoxysilan mit drei Mol-Äquivalenten Oxalsäure und zwei Mol-Äquivalenten 1-(2-Hydroxyethyl)pyrrolidin oder 1-(2-Hydroxyethyl)piperidin in Tetrahydrofuran führte zu den λ 6 Si-Silicaten 1-(2-Hydroxyethyl)pyrrolidinium-tris[oxalato(2Ϫ)]silicat (4) und 1-(2-Hydroxyethyl)piperidinium-tris[oxalato(2Ϫ)]silicat (5). Die verwandten GermaniumVerbindungen 1-(2-Hydroxyethyl)piperidinium-tris[oxalato(2Ϫ)]-germanat (6) und Triethylammonium-tris[oxalato(2Ϫ)]germanat (7) wurden auf analoge Weise durch Umsetzung von Tetramethoxygerman mit drei Mol-Äquivalenten Oxalsäure und zwei Mol-Äqui-

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Dianionic Tris[oxalato(2—)]silicate and Tris[oxalato(2—)]germanate Complexes: Synthesis, Properties, and Structural Characterization in the Solid State and in Solution

Seiler

Burschka

Penka

et al. 2002

Z. anorg. allg. Chem.

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A Zwitterionic Spirocyclic Pentacoordinate Silicon Compound Synthesized in Water by SiO and SiC Bond Cleavage

Tacke¹,

Bertermann²,

Burschka³

et al. 2005

Angewandte Chemie

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The chemistry of higher-coordinate silicon compounds is currently one of the main areas of research in silicon chemistry. [1] We have contributed to this field by systematic studies on zwitterionic l 5 Si-silicates that contain a pentacoordinate (formally negatively charged) silicon atom and a tetracoordinate (formally positively charged) nitrogen atom.[1d] The zwitterions 1, [2] 2, [3] 3, [4] 4, [5] 5, [6] 6, [7] 7, [8] 8, [9] and 9 [10] are examples of this type of compound. Generally, these zwitterionic l 5 Si-silicates are quite sensitive to water and easily undergo hydrolytic SiÀOC, SiÀSC, and SiÀNC bond cleavage. We have now succeeded in synthesizing a zwitterionic l 5 Si-silicate, namely, bis[meso-oxolane-3,4-diolato(2À)][(morpholinio)methyl]silicate (10), that shows remarkable stability in water.[11] Surprisingly, this pentacoordinate silicon compound could even be prepared in aqueous solution by SiÀC bond cleavage. We report herein on the synthesis of 10 and its hydrate 10·H 2 O and their structural characterization in the solid state and in solution.Compound 10 was synthesized according to Scheme 1, either through cleavage of three SiÀO bonds (method a) or through cleavage of two SiÀO bonds and one SiÀC bond (method b), starting with trimethoxy[(morpholino)methyl]-silane (11) [12] (yield 87 %) and dimethoxy[(morpholino)-methyl]phenylsilane (12) [12] (yield 53 %), respectively. As the synthesis according to method b involves a relatively slow SiÀC cleavage reaction as the rate-determining step, [13] product formation was significantly slower than with method a (see Experimental Section). The hydrate 10·H 2 O was synthesized analogously to 10 (Scheme 1, method a) by using water instead of acetonitrile as the solvent and was isolated, after crystallization from water, in 93 % yield as a colorless crystalline solid.The chiral l 5 Si-silicates crystallize in the space groups P2 1

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A Zwitterionic Spirocyclic Pentacoordinate Silicon Compound Synthesized in Water by SiO and SiC Bond Cleavage

et al. 2005

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New Zwitterionic Spirocyclic λ5Si-Silicates with Two Ethane-1,2-diolato(2-), Oxalato(2-), or Benzene-1,2-diolato(2-) Ligands - Synthesis, Structure, and Dynamic Behavior

Cited by 13 publications

References 13 publications

Dianionic Tris[oxalato(2—)]silicate and Tris[oxalato(2—)]germanate Complexes: Synthesis, Properties, and Structural Characterization in the Solid State and in Solution

Dianionic Tris[oxalato(2—)]silicate and Tris[oxalato(2—)]germanate Complexes: Synthesis, Properties, and Structural Characterization in the Solid State and in Solution

A Zwitterionic Spirocyclic Pentacoordinate Silicon Compound Synthesized in Water by SiO and SiC Bond Cleavage

A Zwitterionic Spirocyclic Pentacoordinate Silicon Compound Synthesized in Water by SiO and SiC Bond Cleavage

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