Neuartige zwitterionische λ5-Spirosilicate: Synthese und Kristallstruktur von Bis[l,2-benzoldiolato(2 – )][2-(dimethylammonio)phenyl]silicat sowie Synthese von Bis[2,3-naphthalindiolato(2 – )][2-(dimethylammonio)phenyl]silicat-Hemiacetonitril-Solvat / Novel Zwitterionic λ5-Spirosilicates: Synthesis and Crystal Structure of Bis[1,2-benzenediolato(2–)][2-(dimethylammonio)phenyl]silicate and Synthesis of Bis[2,3-naphthalenediolato(2–)][2-(dimethylammonio)phenyl]silicate Hemiacetonitrile Solvate

• Published in: Zeitschrift für Naturforschung. B, A journal of chemical sciences Vol. 47; no. 10; pp. 1370 - 1376
• Main Authors: Tacke, Reinhold, Wiesenberger, Frank, Lopez-Mras, Angel, Sperlich, Jörg, Mattern, Günter
• Format: Journal Article
• Language: English; Japanese
• Published: Verlag der Zeitschrift für Naturforschung 01.10.1992
• ISSN: 0932-0776; 1865-7117
• DOI: 10.1515/znb-1992-1006

The zwitterionic λ -spirosilicates bis[1,2-benzenediolato(2–)][2-(dimethylammonio)-phenyl]silicate (4) and bis [2,3-naphthalenediolato(2–)][2-(dimethylammonio)phenyl]silicate (5; isolated as 5 · ½CH CN) were synthesized and the crystal structure of 4 was studied by X-ray diffraction. 4 was prepared by reaction of [2-(dimethylamino)phenyl]trimethoxysilane (7) or bis[2-(dimethylamino)phenyl]dimethoxysilane (8) with 1,2-dihydroxybenzene in acetonitrile at room temperature. 5 was synthesized analogously by reaction of 7 or 8 with 2,3-dihydroxynaphthalene. The silanes 7 and 8 were obtained by reaction of tetramethoxysilane (6) with [2-(dimethylamino)phenyl]lithium. The reactions 8 → 4 and 8 → 5 involve a remarkable Si–C cleavage leading to the formation of (dimethylamino)benzene. The pentacoordinate silicon atoms of 4 and 5 are surrounded by four oxygen atoms and one sp hybridized carbon atom. The coordination polyhedron of 4 can be described as a distorted square pyramid, the carbon atom being in the apical position (the structure is distorted by 69,1 % from the trigonal bipyramid towards the square pyramid). In the crystal, 4 forms an intramolecular N-H···O hydrogen bond.