Early-lanthanide(III) acetonitrile–solvento adducts with iodide and noncoordinating anions
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 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.
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1239567
- Report Number(s):
- LA-UR-15-27560
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- AC52-06NA25396
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 54; Journal Issue: 24; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Brown, Jessie L., Davis, Benjamin L., Scott, Brian L., and Gaunt, Andrew J. Early-lanthanide(III) acetonitrile–solvento adducts with iodide and noncoordinating anions. United States: N. p., 2015.
Web. doi:10.1021/acs.inorgchem.5b02291.
Brown, Jessie L., Davis, Benjamin L., Scott, Brian L., & Gaunt, Andrew J. Early-lanthanide(III) acetonitrile–solvento adducts with iodide and noncoordinating anions. United States. https://doi.org/10.1021/acs.inorgchem.5b02291
Brown, Jessie L., Davis, Benjamin L., Scott, Brian L., and Gaunt, Andrew J. Fri .
"Early-lanthanide(III) acetonitrile–solvento adducts with iodide and noncoordinating anions". United States. https://doi.org/10.1021/acs.inorgchem.5b02291. https://www.osti.gov/servlets/purl/1239567.
@article{osti_1239567,
title = {Early-lanthanide(III) acetonitrile–solvento adducts with iodide and noncoordinating anions},
author = {Brown, Jessie L. and Davis, Benjamin L. and Scott, Brian L. and Gaunt, Andrew J.},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.5b02291},
journal = {Inorganic Chemistry},
number = 24,
volume = 54,
place = {United States},
year = {Fri Dec 25 00:00:00 EST 2015},
month = {Fri Dec 25 00:00:00 EST 2015}
}
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