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Steric solvent effect on formation thermodynamics and structure of halogeno complexes of lanthanide(III) ions in N,N-dimethylacetamide

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Steric solvent effect on formation thermodynamics and structure of halogeno complexes of lanthanide(III) ions in N,N-dimethylacetamide

Auteurs : Shin-Ichi Ishiguro ; Kazusuke Kato ; Satoshi Nakasone ; Ryouta Takahashi ; Kazuhiko Ozutsumi

Source :

Journal of the Chemical Society, Faraday Transactions [ 0956-5000 ] ; 1996.

RBID : ISTEX:40CA3F6B2AAB85E690A29B9DD750303069267316

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Abstract

The bromo complexation of a series of LnIII ions (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) has been studied by precise titration calorimetry in N,N-dimethylacetamide (DMA) containing 0.2 mol dm–3(C2H5)4NClO4 as a constant ionic medium at 298 K. The formation of mono-, di- and tri-bromo complexes was established and their formation constants and enthalpies and entropies of formation were determined. With the monobromo complex, both the enthalpy and entropy values are positive and large and exhibit strong dependence on the metal ion. This result in DMA differs markedly from that in N,N-dimethylformamide (DMF). The difference is explained in terms of the formation of an inner-sphere complex in DMA, whilst in DMF a solvent-separated ion pair, or an outer-sphere complex, is formed. The coordination structure of the metal complexes has been evidenced by NMR for yttrium(III) and lanthanum(III) and by EXAFS for thulium(III). It is thus suggested that there is steric hindrance of the solvation of lanthanide(III) ions in DMA. The chloro complexation of LaIII and YIII in DMA was also examined for comparison.

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https://api.istex.fr/document/40CA3F6B2AAB85E690A29B9DD750303069267316/fulltext/pdf

DOI: 10.1039/FT9969201869

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<author wicri:is="90%"><name sortKey="Ishiguro, Shin Ichi" sort="Ishiguro, Shin Ichi" uniqKey="Ishiguro S" first="Shin-Ichi" last="Ishiguro">Shin-Ichi Ishiguro</name>
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<author wicri:is="90%"><name sortKey="Kato, Kazusuke" sort="Kato, Kazusuke" uniqKey="Kato K" first="Kazusuke" last="Kato">Kazusuke Kato</name>
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<author wicri:is="90%"><name sortKey="Nakasone, Satoshi" sort="Nakasone, Satoshi" uniqKey="Nakasone S" first="Satoshi" last="Nakasone">Satoshi Nakasone</name>
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<author wicri:is="90%"><name sortKey="Takahashi, Ryouta" sort="Takahashi, Ryouta" uniqKey="Takahashi R" first="Ryouta" last="Takahashi">Ryouta Takahashi</name>
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<author wicri:is="90%"><name sortKey="Ozutsumi, Kazuhiko" sort="Ozutsumi, Kazuhiko" uniqKey="Ozutsumi K" first="Kazuhiko" last="Ozutsumi">Kazuhiko Ozutsumi</name>
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<series><title level="j">Journal of the Chemical Society, Faraday Transactions</title>
<title level="j" type="abbrev">J. Chem. Soc., Faraday Trans.</title>
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<profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Acetyl methyl group</term>
<term>Apparent enthalpy values</term>
<term>Atomic number</term>
<term>Bromide</term>
<term>Bromo</term>
<term>Bromo complexation</term>
<term>Bromo complexes</term>
<term>Calorimetric</term>
<term>Calorimetric data points</term>
<term>Calorimetric titration curves</term>
<term>Chem</term>
<term>Chemical shifts</term>
<term>Chloro complexation</term>
<term>Chloro complexes</term>
<term>Complexation</term>
<term>Coordination number</term>
<term>Dalton trans</term>
<term>Direct bond</term>
<term>Enthalpy</term>
<term>Entropy values</term>
<term>Exafs</term>
<term>Exafs spectra</term>
<term>Experimental data</term>
<term>Experimental points</term>
<term>Faraday trans</term>
<term>First coordination sphere</term>
<term>Formation constants</term>
<term>Halide ions</term>
<term>Halogeno complexes</term>
<term>Ionic medium</term>
<term>Lanthanide</term>
<term>Lanthanide series</term>
<term>Metal ions</term>
<term>Metal perchlorate</term>
<term>Metal perchlorate solution</term>
<term>Metal systems</term>
<term>Mole fraction</term>
<term>Molecular sieves</term>
<term>Other hand</term>
<term>Perchlorate</term>
<term>Perchlorate solution</term>
<term>Perchloric acid</term>
<term>Reaction enthalpies</term>
<term>Sample solution</term>
<term>Sample solutions</term>
<term>Scientific research</term>
<term>Single peak</term>
<term>Solid lines</term>
<term>Solution chemistry</term>
<term>Solvate crystals</term>
<term>Solvent coordination number</term>
<term>Solvent molecules</term>
<term>Standard deviations</term>
<term>Steric hindrance</term>
<term>Structural parameters</term>
<term>Structure parameters</term>
<term>Tetrabutylammonium bromide</term>
<term>Thermodynamic irregularity</term>
<term>Thermodynamic parameters</term>
<term>Titration</term>
<term>Titration point</term>
<term>Trans</term>
<term>Znorg</term>
</keywords>
<keywords scheme="Teeft" xml:lang="en"><term>Acetyl methyl group</term>
<term>Apparent enthalpy values</term>
<term>Atomic number</term>
<term>Bromide</term>
<term>Bromo</term>
<term>Bromo complexation</term>
<term>Bromo complexes</term>
<term>Calorimetric</term>
<term>Calorimetric data points</term>
<term>Calorimetric titration curves</term>
<term>Chem</term>
<term>Chemical shifts</term>
<term>Chloro complexation</term>
<term>Chloro complexes</term>
<term>Complexation</term>
<term>Coordination number</term>
<term>Dalton trans</term>
<term>Direct bond</term>
<term>Enthalpy</term>
<term>Entropy values</term>
<term>Exafs</term>
<term>Exafs spectra</term>
<term>Experimental data</term>
<term>Experimental points</term>
<term>Faraday trans</term>
<term>First coordination sphere</term>
<term>Formation constants</term>
<term>Halide ions</term>
<term>Halogeno complexes</term>
<term>Ionic medium</term>
<term>Lanthanide</term>
<term>Lanthanide series</term>
<term>Metal ions</term>
<term>Metal perchlorate</term>
<term>Metal perchlorate solution</term>
<term>Metal systems</term>
<term>Mole fraction</term>
<term>Molecular sieves</term>
<term>Other hand</term>
<term>Perchlorate</term>
<term>Perchlorate solution</term>
<term>Perchloric acid</term>
<term>Reaction enthalpies</term>
<term>Sample solution</term>
<term>Sample solutions</term>
<term>Scientific research</term>
<term>Single peak</term>
<term>Solid lines</term>
<term>Solution chemistry</term>
<term>Solvate crystals</term>
<term>Solvent coordination number</term>
<term>Solvent molecules</term>
<term>Standard deviations</term>
<term>Steric hindrance</term>
<term>Structural parameters</term>
<term>Structure parameters</term>
<term>Tetrabutylammonium bromide</term>
<term>Thermodynamic irregularity</term>
<term>Thermodynamic parameters</term>
<term>Titration</term>
<term>Titration point</term>
<term>Trans</term>
<term>Znorg</term>
</keywords>
<keywords scheme="Wicri" type="topic" xml:lang="fr"><term>Recherche scientifique</term>
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<front><div type="abstract">The bromo complexation of a series of LnIII ions (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) has been studied by precise titration calorimetry in N,N-dimethylacetamide (DMA) containing 0.2 mol dm–3(C2H5)4NClO4 as a constant ionic medium at 298 K. The formation of mono-, di- and tri-bromo complexes was established and their formation constants and enthalpies and entropies of formation were determined. With the monobromo complex, both the enthalpy and entropy values are positive and large and exhibit strong dependence on the metal ion. This result in DMA differs markedly from that in N,N-dimethylformamide (DMF). The difference is explained in terms of the formation of an inner-sphere complex in DMA, whilst in DMF a solvent-separated ion pair, or an outer-sphere complex, is formed. The coordination structure of the metal complexes has been evidenced by NMR for yttrium(III) and lanthanum(III) and by EXAFS for thulium(III). It is thus suggested that there is steric hindrance of the solvation of lanthanide(III) ions in DMA. The chloro complexation of LaIII and YIII in DMA was also examined for comparison.</div>
</front>
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Steric solvent effect on formation thermodynamics and structure of halogeno complexes of lanthanide(III) ions in N,N-dimethylacetamide

Steric solvent effect on formation thermodynamics and structure of halogeno complexes of lanthanide(III) ions in N,N-dimethylacetamide

Source :

Descripteurs français

English descriptors

Abstract

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