Investigation of alkali metal-water interactions in acetonitrile

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. © 1991.

Department(s)

Chemistry and Biochemistry

Document Type

Article

DOI

https://doi.org/10.1016/S0020-1693(00)83002-9

Publication Date

5-1-1991

Journal Title

Inorganica Chimica Acta

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