Early-lanthanide(III) acetonitrile–solvento adducts with iodide and noncoordinating anions

Brown, Jessie L.; Davis, Benjamin L.; Scott, Brian L.; Gaunt, Andrew J.

doi:10.1021/acs.inorgchem.5b02291

Title: Early-lanthanide(III) acetonitrile–solvento adducts with iodide and noncoordinating anions

Journal Article · Fri Dec 25 00:00:00 EST 2015 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.5b02291· OSTI ID:1239567

Brown, Jessie L. ^[1]; Davis, Benjamin L. ^[2]; Scott, Brian L. ^[2]; Gaunt, Andrew J. ^[2]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Transylvania Univ., Lexington, KY (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

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 La³⁺ 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. Furthermore, 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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Research Organization:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1239567

Report Number(s):: LA-UR-15-27560

Journal Information:: Inorganic Chemistry, Vol. 54, Issue 24; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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