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Early-Lanthanide(III) Acetonitrile-Solvento Adducts with Iodide and Noncoordinating Anions
Jessie L Brown1, Benjamin L Davis, Brian L Scott
1Division of Natural Sciences and Mathematics, Transylvania University , Lexington, Kentucky 40508, United States.
Abstract:
Dissolution of LnI3 (Ln = La, Ce) in acetonitrile (MeCN) results in the highly soluble solvates LnI3(MeCN)5 [Ln = La (1), Ce (2)] in good yield. The ionic complex [La(MeCN)9][LaI6] (4), containing a rare homoleptic La(3+) cation and anion, was also isolated as a minor product. Extending this chemistry to NdI3 results in the consistent formation of the complex ionic structure [Nd(MeCN)9]2[NdI5(MeCN)][NdI6][I] (3), which contains an unprecedented pentaiodide lanthanoid anion. Also described is the synthesis, isolation, and structural characterization of several homoleptic early-lanthanide MeCN solvates with noncoordinating anions, namely, [Ln(MeCN)9][AlCl4]3 [Ln = La (5), Ce (6), Nd (7)]. Notably, complex 6 is the first homoleptic cerium MeCN solvate reported to date. All reported complexes were structurally characterized by X-ray crystallography, as well as by IR spectroscopy and CHN elemental analysis. Complexes 1-3 were also characterized by thermogravimetric analysis coupled with mass spectrometry to further elucidate their bulk composition in the solid-state.
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