NDLI: Polyoxopalladates Encapsulating Yttrium and Lanthanide Ions, $[X^{III}Pd^{II}_{12}(AsPh)_{8}O_{32}]^{5−}$ (X=Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)

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Polyoxopalladates Encapsulating Yttrium and Lanthanide Ions, $[X^{III}Pd^{II}_{12}(AsPh)_{8}O_{32}]^{5−}$ (X=Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)

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Polyoxopalladates Encapsulating Yttrium and Lanthanide Ions, $[X^{III}Pd^{II}_{12}(AsPh)_{8}O_{32}]^{5−}$ (X=Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Poblet, Josep M. Carbó, Jorge J. Nadjo, Louis Antonova, Nadya S. Izarova, Natalya V. Dalal, Naresh S. Biboum, Rosa Ngo Kortz, Ulrich Keita, Bineta Ramachandran, Vasanth Barsukova, Maria
Description	Author Affiliation: Barsukova M ( School of Engineering and Science, Jacobs University, P.O. Box 750 561, 28725 Bremen, Germany.)
Abstract	A series of novel yttrium- and lanthanide-containing heteropolyoxopalladates have been prepared and isolated as hydrated sodium salts, $Na_{5}[X^{III}Pd^{II}_{12}(AsPh)_{8}O_{32}]⋅y H_{2}O$ (X=Y (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Ho (9), Er (10), Tm (11), Yb (12), Lu (13); y=15–27). The polyanions $[X^{III}Pd^{II}_{12}(AsPh)_{8}O_{32}]^{5−}$ consist of a cuboid framework of twelve $Pd^{II}$ ions with eight phenylarsonate heterogroups located at the vertices and a central guest ion X. The compounds 1–13 have been prepared in a simple one-pot self-assembly reaction of $Pd(CH_{3}COO)_{2},$ phenylarsonic acid and the respective salt of the element X in 0.5 M aqueous sodium acetate solution (pH 6.9), and characterized in the solid state by single-crystal X-ray diffraction, elemental and thermogravimetric (TGA) analyses, and IR spectroscopy. It was demonstrated that small, medium, and also large lanthanide ions can be incorporated in the center of the novel heteropolypalladate $[X^{III}Pd^{II}_{12}(AsPh)_{8}O_{32}]^{5−}.$ The LnO bond lengths follow the expected trend decreasing from left to right in the lanthanide series. This indicates that the $\{Pd^{II}_{12}O_{32}\}$ shell can adjust to the coordination requirements of the encapsulated guest cation. Compounds 3 and 5 were selected for electrochemical studies. Their cyclic voltammetry in a lithium acetate buffer at pH 5.9 showed a $Pd^{0}$ deposition process on the glassy carbon electrode surface. Coulometry indicated that all $Pd^{II}$ centers were reduced to $Pd^{0}.$ The film was stable and could be taken out of the deposition medium and characterized in pure pH 5.9 buffer. Magnetic susceptibility and EPR measurements were carried out on 5 and 6. The former was confirmed to be diamagnetic and the latter strongly paramagnetic with a S=7/2 ground state. DFT calculations for some of the polyoxometalates have been also performed.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	30
Volume Number	16
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2010-08-09
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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