205Tl NMR studies: Ion pairing of Tl+ and (CH3)2Tl+ with NO 3 − and ClO 4 − in various solvents |
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Authors: | Richard W. Briggs Kenneth R. Metz James F. Hinton |
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Affiliation: | (1) Department of Chemistry, University of Arkansas, 72701 Fayetteville, Arkansas |
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Abstract: | The concentration dependence of the205Tl chemical shifts of Tl+ and of (CH3)2Tl+ ions was determined in several solvents with NO3– and ClO4– counterions. In general, increased ion pairing caused a low-frequency shift of the205Tl resonance, with the exceptions of (CH3)2TlNO3 inn-butylamine and TlNO3 in N,N-dimethylformamide (DMF) and in hexamethylphosphorotriamide (HMPA). In HMPA,205Tl linewidths of both Tl+ and (CH3)2Tl+ increased dramatically with dilution below 0.1M. Analysis of the data allowed ion-pair formation constants and205Tl chemical shifts for the ion-paired cation and for the free (solvated) cation to be estimated for some of the solvents. |
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Keywords: | Ion pairs solvation nonaqueous solvents thallium-205 NMR ion-pair formation constants |
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