Infrared spectral studies of ion association in nonaqueous solutions of cyanide salts with consequences for their nucleophilic reactivity |
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Authors: | A. Loupy J. Corset |
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Affiliation: | (1) Groupe de Recherches No. 12 du CNRS, 94320 Thiais, France;(2) Service de Spectrochimie Infrarouge et Raman du CNRS, 94320 Thiais, France |
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Abstract: | An infrared spectrometric study of alkali metal and tetraphenylarsonium cyanide (As4CN) solutions in DMSO or DMF shows that even for concentrations of 0.1M a large proportion of the ions are associated. The order of basicity established through methanol (OH) frequency shifts is CN–>Cl–>Br–. Addition of common ions or cyclic polyether to these solutions, as well as correlations between the (CN–) frequencies and those of the (CN) bands of CH3CN bonded to the same cations, suggests assignments of the observed bands to solvated contact ion pairs M+ CN–, triple ions M+ CN– M+, and aggregates (M+ CN)n–. The nucleophilic reactivity of these salts is related to the structure of these solutions.This article is taken in part from the thesis of A. Loupy, University Paris-Sud Orsay, April 9, 1975, CNRS thesis order No. AO 10102. |
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Keywords: | Infrared study ionic association nucleophilic reactivity dimethyl sulfoxide dimethylformamide tetraphenylarsonium cyanide alkali metal cyanides |
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