Investigation of Alkali Metal-Water Interactions in Acetonitrile

Document Type

Article

Publication Date

5-1991

Publication Source

Inorganica Chimica Acta

Abstract

The exchange of acetonitrile into and out of the coordination sphere of alkali metal ions is fast on the NMR time scale and slow on the vibrational time scale. This results in separate infrared and Raman spectra for coordinated and non-coordinated solvents in solutions of alkali metal salts in acetonitrile. The 1H NMR spectra, on the other hand, are averages of coordinated and non-coordinated environoments. Addition of water to solutions of alkali metal salts in acetonitrile indicates that the cation is again preferentially solvated by water. The water completely replaces acetonitrile in the lithium coordination sphere until four waters have been added. Water also displaces the first acetonitrile from the coordination sphere of sodium and potassium ions. However, when additional water is added there is an equilibrium mixture of various species. Spectroscopic study of these solutions allows one to gain insights about the energetics and geometry of the cation. Experimental results from NMR, Raman and IR measurements along with extended Hückel molecular orbital calculations are used to discuss the alkali metal cation- water-acetonitrile system.

Inclusive pages

113-118

ISBN/ISSN

0020-1693

Comments

We wish to thank Wright Patterson Air Force Base Aeropropulsion Laboratory for the support of. this work (Contract No. F33615-86-C-2712). NMR and Raman instrumentation was purchased with partial support from the University of Dayton Research Council and the Ohio Board of Regents.

Publisher

Elsevier

Volume

183

Peer Reviewed

yes

Issue

1

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