Synthesis and Characterization of Homoleptic Rare Earth Nitrato Complexes with the Quaternary Ammonium Cations Et4N+ and nPr4N+

Tarlton, Michael L.; Wilson, Richard E.

doi:10.1002/ejic.202200506

Synthesis and Characterization of Homoleptic Rare Earth Nitrato Complexes with the Quaternary Ammonium Cations Et₄N⁺ and ⁿPr₄N⁺

Journal Article · Wed Sep 14 00:00:00 EDT 2022 · European Journal of Inorganic Chemistry

DOI:https://doi.org/10.1002/ejic.202200506· OSTI ID:2217023

Tarlton, Michael L. ^[1]; ^[1]

Argonne National Laboratory (ANL), Argonne, IL (United States)

Two periodic series of homoleptic rare earth nitrato com plexes, [R₄N]_x[M(NO₃)_y](M = La-Nd, Sm-Lu, Y); R = Et, ^$$n$$Pr; x = 2-3; y = 5-6) have been synthesized, and charac terized by single crystal X-ray diffraction, IR and Raman spectroscopy, comparing the solid state speciation of the nitrate ions as a function of lanthanide ion and quarternary ammonium cation. The series of the form [Et₄N]₃[Ln(NO₃)₆] crystallizes in the rhombohedral space group $$R$$$\bar{3}$$, as a twelve-coordinate hexanitrato complex [Et₄N]₃[Ln(NO₃)₆] with cocrystallized HNO₃ for La, Pr, and Nd. For Ce, a distinct orthorhombic phase retaining the same formula, [Et₄N]₃[Ce(NO₃)₆] is isolated in the absence of HNO₃ to prevent oxidation of the Ce(III) to Ce(IV) in nitric acid. A ten-coordinate pentanitrato complex, [Et₄N]₂[Ln(NO₃)₅], in monoclinic symmetry forms for the remainder of the series, and for Y(III). The entire series crystallized in the presence of [^$$n$$Pr₄N]⁺ counterions forms a pentanitrato complex [^$$n$$Pr₄N]₂[M(NO₃)₅] in the orthorhombic space group, $Pccn$. In conclusion, analysis of trends in the structural and spectroscopic characteristics of these series reveal insight into the structure directing influences of both the lanthanide contraction and the quarternary ammonium cations.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2217023

Alternate ID(s):: OSTI ID: 1903064

Journal Information:: European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Journal Issue: 35 Vol. 2022; ISSN 1434-1948

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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CCDC 2193070: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm269 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193071: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm27b The current record is supplemented by this dataset	dataset	January 2022
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CCDC 2193078: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm2gk The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193079: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm2hl The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193080: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm2jm The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193081: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm2kn The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193083: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm2mq The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193084: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm2nr The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193087: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm2rv The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193113: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm3lq The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193114: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm3mr The current record is supplemented by this dataset	dataset	January 2023
CCDC 2193115: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm3ns The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193125: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm3z3 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193127: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm416 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193128: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm427 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193129: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm438 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193130: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm449 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193131: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm45b The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193132: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm46c The current record is supplemented by this dataset	dataset	January 2022
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CCDC 2193136: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm4bh The current record is supplemented by this dataset	dataset	January 2022
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CCDC 2193244: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm7t2 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193245: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cm7v3 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193390: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cmdjy The current record is supplemented by this dataset	dataset	January 2022
CCDC 2193397: Experimental Crystal Structure Determination L., Tarlton, Michael; E., Wilson, Richard https://doi.org/10.5517/ccdc.csd.cc2cmdr5 The current record is supplemented by this dataset	dataset	January 2022
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Synthesis and Characterization of Homoleptic Rare Earth Nitrato Complexes with the Quaternary Ammonium Cations Et4N+ and nPr4N+

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Synthesis and Characterization of Homoleptic Rare Earth Nitrato Complexes with the Quaternary Ammonium Cations Et₄N⁺ and ⁿPr₄N⁺