Solvation of Copper(II) Ions in Liquid Ammonia
- 1 January 1996
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 35 (19) , 5642-5645
- https://doi.org/10.1021/ic960475k
Abstract
X-ray absorption fine structure (XAFS) measurements have been performed at −50 °C on a 0.4 mol dm-3 copper(II) nitrate solution in liquid ammonia. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the coordination number and bond distances for the solvated copper(II) ion in solution. The equatorial ammonia nitrogens are located 2.00 Å from the copper and the axial nitrogen 2.19 Å from the copper. However, it was not possible from the EXAFS analysis alone to conclude whether there was one or two axial nitrogens. Therefore, X-ray absorption near-edge structure (XANES) spectroscopy was combined with discrete variational Xα (DV−Xα) molecular orbital calculations for a series of five- and six-coordinated models to determine the coordination number and the geometry. The experimental XANES spectrum was best reproduced by a model where the copper(II) ion is pentacoordinated in liquid ammonia in a square pyramidal geometry with the copper(II) ion lifted above the average nitrogen plane.Keywords
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