On the detection by EXAFS spectroscopy of multimeric species and of complex anions in diethylether and diethylcarbonate |
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Authors: | J. Goulon C. Goulon-Ginet M. Chabanel |
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Affiliation: | (1) Laboratoire de Chimie Théorique, Université de NANCY I, 54137 Nancy, France;(2) Laboratoire pour l'Utilisation du Rayonnement Electromagnetique, Laboratoire Propre du CNRS, Associé à l'Université de Paris Sud-Orsay, Bâtiment 209C, 91405 Orsay, France;(3) Laboratoire de Spectrochimie des Ions, Université de Nantes-2, Rue de la Houssinière, 44072 Nantes, France |
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Abstract: | EXAFS spectroscopy has been shown to be a reliable tool for detecting the formation in solutions of molecular associations (LiBr)n where n is solvent dependent. The signal Br*...Br observed at 3.87 Å confirms the formation of tetrameric species (n=4) in diethylether (Et2O) but only of dimers (n=2) in diethylcarbonate. Another signal observed at 2.45 Å has·been attributed to the pair Br*...Li. The study of Li2MBr4–Et2O solutions (M=Co, Cu, Zn) also affords new evidence for the formation of complex anions MBr4 2– but the spectra obtained at the bromine or metalK-edges for LiZnBr3–Et2O solutions seems to indicate the formation of more complex aggregates (LiMBr3)q. While the signal of the shell Br*...Br is found quite intense for the reference CBr4–Et2O system, it does not appear for the MBr42– complex except for CuBr42– where the Jahn-Teller effect might rigidify a distorted tetrahedral structure.Presented, in part, at the VIIth International Conference on Non-Aqueous Solutions, Regensburg, West Germany, Ausgust 1980. |
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Keywords: | EXAFS aprotic solvents diethylether diethylcarbonate ionic aggregates lithium bromide complex bromides |
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