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(Ammoniomethyl)bis[salicylato(2−)-O1,O2]silicates:  Zwitterionic Spirocyclic λ5Si-Silicates with Two Six-Membered SiO2C3 Ring Systems

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journal contribution
posted on 03.04.1998 by Reinhold Tacke, Joachim Heermann, Melanie Pülm, Ingo Richter
The zwitterionic spirocyclic λ5Si-silicate (morpholiniomethyl)bis[salicylato(2−)-O1,O2]silicate (5) was synthesized by reaction of trimethoxy(morpholinomethyl)silane and dimethoxy(morpholinomethyl)phenylsilane, respectively, with salicylic acid (molar ratio 1:2) in acetonitrile at room temperature. Bis[salicylato(2−)-O1,O2][(2,2,6,6-tetramethylpiperidinio)methyl]silicate (6) was obtained analogously, starting from trimethoxy[(2,2,6,6-tetramethylpiperidino)methyl]silane. Compound 5 was isolated as a crystalline product consisting of enantiomorphic crystals, each containing exclusively zwitterions with the same absolute configuration. Crystallization of this product from acetonitrile yielded the crystalline solvate 5·CH3CN (crystals containing a 1:1 mixture of enantiomers with opposite absolute configuration). Compounds 5 (Δ-enantiomer), 5·CH3CN (racemate), and 6 (racemate) were structurally characterized by single-crystal X-ray diffraction. The spirocyclic frameworks of 5 and 6 are built up by two six-membered SiO2C3 ring systems. The zwitterions in the crystal of 5, 5·CH3CN, and 6 contain a pentacoordinate (formally negatively charged) silicon atom (SiO4C skeleton) and a tetracoordinate (formally positively charged) nitrogen atom. The coordination polyhedra around the silicon atoms are distorted trigonal bipyramids, the axial positions being occupied by the carboxylate oxygen atoms. Solid-state MAS NMR studies revealed the following isotropic 29Si chemical shifts:  δ −120.6 (5), −123.1 (5·CH3CN), −120.4 (6). The zwitterion 6 exists also in solution (CDCl3; 1H, 13C, and 29Si NMR studies).