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Your search keyword '"Tzschach, A."' showing total 40 results
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24. ChemInform Abstract: In situ Nucleophilic Activation in the Propellane 5-Chloro-1-aza-5-silatricyclo(3.3.3.01,5)undecane and Its Hydrolysis in Solution

Author

Rudolph Willem, Marcel Gielen, Andreas Tzschach, Klaus Jurkschat, Henri Pepermans, and M. Dargatz

Subjects
Hexacoordinate, General Medicine, Reversible reaction, law.invention, Propellane, chemistry.chemical_compound, chemistry, Nucleophile, law, Computational chemistry, Proton NMR, Undecane, Walden inversion, Chlorosilane
Abstract

The compound 5-chloro-1-aza-5-silatricyclo[3.3.3.01,5]undecane (C9H18NSiCl) combines with water to form an association complex with the formula C9H18NSiCl·H2O. Proton NMR studies at various temperatures, concentrations and magnetic fields indicate that this compound exists in solution as an equilibrium mixture of the initial chloride and its association complex with water, a structure for which is proposed. Evidence is provided against a rigid hexacoordinate complex. The equilibrium is shown to correspond to a reversible hydrolysis of C9H18NSiCl which is nucleophilically activated by the intramolecularly coordinating nitrogen present in situ. The reverse reaction is the decomposition of the association complex C9H18NSiCl·H2O to C9H18NSiCl and free water. As a consequence, this paper presents a reversible hydrolysis of a chlorosilane interconverting two directly observable pentacoordinate species without addition of an external nucleophile, and proceeding with retention of configuration at the silicon atom. We further argue that this reaction cannot proceed through a rigid hexacoordinate octahedral intermediate, but could proceed through two non-rigid species, the averaged dynamic behaviour of which is identical to a non-octahedral hexacoordinate transition state.

Published
1988
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26. ChemInform Abstract: Synthesis, Crystal and Molecular Structure of O(Si(CH2CH2CH2)3N)2, an Oxygen-Bridged Bis(tricarbasilatrane)

Author

Andreas Tzschach, Klaus Jurkschat, Jacqueline Meunier-Piret, and M. Van Meerssche

Subjects
Diffraction, Crystal, Trigonal bipyramidal molecular geometry, Crystallography, Silicon, chemistry, Yield (chemistry), Intramolecular force, chemistry.chemical_element, Molecule, General Medicine, Nuclear magnetic resonance spectroscopy
Abstract

The hydrolysis of ClSi(CH2CH2CH2)3N gives the compound O[Si(CH2CH2CH2)3N]2 in high yield. Its structure has been investigated by 1H, 13C and 29Si NMR spectroscopy and X-ray diffraction. The compound crystallizes in the cubic space group Pa 3 . The unit cell with a 12.701(13) A and V 2048.9 A3, contains four molecules. The structure was refined to a final R value of 0.092. The intramolecular SiN distance is 2.477 A. The silicon atoms have a distorted trigonal bipyramidal configuration.

Published
1987
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