Structural studies of lanthanide nitrate–N,N′-dimethyl-N,N′-diphenylpyridine-2,6-dicarboxyamide complexes

Fujiwara, Asako; Nakano, Yoshiharu; Yaita, Tsuyoshi; Okuno, Kenji

doi:10.1016/j.jallcom.2007.02.056

Cited by 17 publications

(5 citation statements)

References 37 publications

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“…The structures of N,N,N ,N -tetraethylpyridine-2,6-dicarboxamide (1), [25] N,N -dimethyl-N,N -diphenylpyridine-2,6-dicarboxamide (2), [26] N,N -diethyl-N,Ndiphenyl-pyridine-2,6-dicarboxamide (4), [27] and N,N -bis(4-methylphenyl)-pyridine-2,6-dicarboxamide [28] obtained by X-ray diffraction analysis were described. A molecule of Downloaded by [University of Regina] at 03:03 25 August 2014 N,N -bis(4-methylphenyl)-pyridine-2,6-dicarboxamide contains only one substituent at the nitrogen atoms of each amide group and, hence, no steric hindrances exist for the formation of the most stable almost planar anti-anti-conformation with the carbonyl oxygen atoms mostly remote from each other.…”

Section: Structures Of Pyridinedicarboxylic Acid Diamidesmentioning

confidence: 99%

Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

Ustynyuk

Gloriozov

Kalmykov

et al. 2014

Solvent Extraction and Ion Exchange

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This article presents a general approach to solving the urgent practical problem of separation of 4f-(lanthanides, Ln 3+ ) and 5f-elements (actinides, An 3+ ) very similar in properties based on the DFT quantum-chemical supercomputer simulation of Ln 3+ and An 3+ complexes with polydentate nitrogen-containing heterocyclic ligands. The method allows to calculate the geometry parameters of ligands and complexes and the metal to ligand binding energies with accuracy, permitting a direct comparison of calculation results with the experimental data, and estimate selectivity factors for separation of Eu 3+ /Am 3+ model pair cations (SF Am/Eu ) in extraction experiments on a semi-quantitative level. The applicability of the method and the approach demonstrated by DFT-modeling (nonempirical PBE functional, extended relativistic full-electron basis set) of a large series of diamides of pyridine-2,6-dicarboxylic (dipicolinic) acid (L) with different substituents at the amide nitrogen atoms and in the pyridine cycle, as well as their complexes [LM] 3+ , (H 2 O) n M(NO 3 ) 3 (n = 3, 4), and LM(NO 3 ) 3 (M = Eu, Am).Based on the theoretical analysis a new model is proposed that describes the mechanism of Ln 3+ and An 3+ extraction in two-phase system highly acidic water solution-organic solvent, according to which the formation of An 3+ and Ln 3+ complexes occurs at the water/organic interface as a substitution reaction of hydroxonium ion in a cavity of a protonated ligand for the metal cation.Calculation results confirm the experimentally established higher extraction ability of dipicolinic acid diamides containing one aryl and one alkyl substituent at the amide nitrogen atoms compared to the N,N,N ,N -tetraalkyl diamides ("effect of anomalous aryl strengthening"). Based on the simulation results the structure of the modified ligand L suggested that it should ensure maximum An 3+ /Ln 3 separation selectivity in the series of dipicolinic acid diamides.

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Section: Structures Of Pyridinedicarboxylic Acid Diamidesmentioning

confidence: 99%

Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

Ustynyuk

Gloriozov

Kalmykov

et al. 2014

Solvent Extraction and Ion Exchange

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“…The differences in metal‐ligand complex formation for ligands with different substituents appeared in solvent extraction should also be seen in structures of solid crystals. To date, all studies devoted to the structures of 2,6‐pyridinecarboxamide complexes with nitrates of actinides and lanthanides were performed using ligands with both alkyl and aryl substituents. All other published complexes of dipicolinamides with metals had weakly coordinating perchlorate of triflate as a counterion and they greatly differ from complexes with strong coordinating nitrate ion .…”

Section: Introductionmentioning

confidence: 99%

Complexes of Uranyl Nitrate with 2,6-Pyridinedicarboxamides: Synthesis, Crystal Structure, and DFT Study

Alyapyshev

Бабаин

Ткаченко

et al. 2017

Z. Anorg. Allg. Chem.

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“…Ried and Neidhardt studied “hydrogenolysis” of the N -methyl compound 7a and related quinoline carboxylic acids upon reaction with lithium aluminium hydride 27 . The N -methyl ( 7a ) and N -ethyl ( 7b ) analogues have been used to generate metal complexes 17 18 and in metal extraction experiments 19 20 21 , while Dobler et al conducted computational experiments to describe the interaction between ligands of this type and lanthanide cations 28 . Kapoor and coworkers recently reported synthesis and structural characterisation of related thioamide derivatives 29 .…”

Section: Resultsmentioning

confidence: 99%

“…These compounds are of interest for potential application in molecular switches and devices that exploit the controlled cis / trans isomerisation of the amide bond 14 15 16 . They have demonstrated utility in coordination chemistry with transition metals 17 and lanthanoids 18 , and have been applied to radionucleotide extraction 19 20 21 .…”

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confidence: 99%

Synthesis and structural characterisation of amides from picolinic acid and pyridine-2,6-dicarboxylic acid

Devi

Barry

Houlihan

et al. 2015

Sci Rep

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Coupling picolinic acid (pyridine-2-carboxylic acid) and pyridine-2,6-dicarboxylic acid with N-alkylanilines affords a range of mono- and bis-amides in good to moderate yields. These amides are of interest for potential applications in catalysis, coordination chemistry and molecular devices. The reaction of picolinic acid with thionyl chloride to generate the acid chloride in situ leads not only to the N-alkyl-N-phenylpicolinamides as expected but also the corresponding 4-chloro-N-alkyl-N-phenylpicolinamides in the one pot. The two products are readily separated by column chromatography. Chlorinated products are not observed from the corresponding reactions of pyridine-2,6-dicarboxylic acid. X-Ray crystal structures for six of these compounds are described. These structures reveal a general preference for cis amide geometry in which the aromatic groups (N-phenyl and pyridyl) are cis to each other and the pyridine nitrogen anti to the carbonyl oxygen. Variable temperature 1H NMR experiments provide a window on amide bond isomerisation in solution.

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Structural studies of lanthanide nitrate–N,N′-dimethyl-N,N′-diphenylpyridine-2,6-dicarboxyamide complexes

Cited by 17 publications

References 37 publications

Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

Complexes of Uranyl Nitrate with 2,6-Pyridinedicarboxamides: Synthesis, Crystal Structure, and DFT Study

Synthesis and structural characterisation of amides from picolinic acid and pyridine-2,6-dicarboxylic acid

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