Low‐temperature ionization of neutral hexacoordinate to ionic pentacoordinate silicon complexes. Unusual temperature, solvent and substituent effects
Journal of Physical Organic Chemistry2002Vol. 15(12), pp. 831–834
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Abstract
Abstract Neutral hexacoordinate complexes of silicon ( 1 ) ionize to pentacoordinate siliconium chloride salts ( 2 ) in CH 2 Cl 2 , CHCl 3 or CHFCl 2 solutions. 29 Si NMR measurements prove that the extent of ionization increases as the temperature of the solution is lowered. The ionizations are slightly exothermic, and have negative entropies. It is shown that increased solvent polarity drives the reaction to the ionic side, i.e. that ion solvation is responsible for the ionization. The lack of a common‐ion effect on addition of tetrabutylammonium chloride indicates the formation of unseparated ion pairs. Copyright © 2002 John Wiley & Sons, Ltd.
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