Gd7I12Zn: a group 12 atom in the octahedral Gd6 Cluster.

Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, D-70569 Stuttgart, Germany.
Inorganic Chemistry (Impact Factor: 4.59). 07/2008; 47(11):4656-60. DOI: 10.1021/ic800024n
Source: PubMed

ABSTRACT The title compound was synthesized from Gd, GdI 3 and Zn under Ar atmosphere at 850 degrees C. It crystallizes in the space group R3 (No. 148) with lattice constants a=15.686(1) A and c=10.4882(8) A. The structure features isolated Zn-centered Gd 6 octahedra with all edges and corners capped by I atoms. The disorder of the Gd atoms is rationalized via electron microscopic techniques. A computational analysis using the extended Hückel method has been carried out in order to understand the bonding of this compound. The structure of isotypic La 7I12Co is also remarked (a=16.040(1) A and c=10.905(2) A).

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    ABSTRACT: Reactions of CeIII(NO3)3⋅6 H2O or (NH4)2[CeIV(NO3)6] with Mn-containing starting materials result in seven novel polynuclear Ce or Ce/Mn complexes with pivalato (tBuCO) and, in most cases, auxiliary N,O- or N,O,O-donor ligands. With nuclearities ranging from 6–14, the compounds present aesthetically pleasing structures. Complexes [CeIV6(μ3-O)4(μ3-OH)4(μ-O2CtBu)12] (1), [CeIV6MnIII4(μ4-O)4(μ3-O)4(O2CtBu)12(ea)4(OAc)4]⋅4 H2O⋅4 MeCN (ea−=2-aminoethanolato; 2), [CeIV6MnIII8(μ4-O)4(μ3-O)8(pye)4(O2CtBu)18]2[CeIV6(μ3-O)4(μ3-OH)4(O2CtBu)10(NO3)4] [CeIII(NO3)5(H2O)]⋅21 MeCN (pye−=pyridine-2-ethanolato; 3), and [CeIV6CeIII2MnIII2(μ4-O)4(μ3-O)4(tbdea)2(O2CtBu)12(NO3)2(OAc)2]⋅4 CH2Cl2 (tbdea2−=2,2′-(tert-butylimino]bis[ethanolato]; 4) all contain structures based on an octahedral {CeIV6(μ3-O)8} core, in which many of the O-atoms are either protonated to give (μ3-OH)− hydroxo ligands or coordinate to further metal centers (MnIII or CeIII) to give interstitial (μ4-O)2− oxo bridges. The decanuclear complex [CeIV8CeIIIMnIII(μ4-O)3(μ3-O)3(μ3-OH)2(μ-OH)(bdea)4(O2CtBu)9.5(NO3)3.5(OAc)2]⋅1.5 MeCN (bdea2−=2,2′-(butylimino]bis[ethanolato]; 5) contains a rather compact CeIV7 core with the CeIII and MnIII centers well-separated from each other on the periphery. The aggregate in [CeIV4MnIV2(μ3-O)4(bdea)2(O2CtBu)10(NO3)2]⋅4 MeCN (6) is based on a quasi-planar {MnIV2CeIV4(μ3-O)4} core made up of four edge-sharing {MnIVCeIV2(μ3-O)} or {CeIV3(μ3-O)} triangles. The structure of [CeIV3MnIV4MnIII(μ4-O)2(μ3-O)7(O2CtBu)12(NO3)(furan)]⋅6 H2O (7⋅6 H2O) can be considered as {MnIV2CeIV2O4} and distorted {MnIV2MnIIICeIVO4} cubane units linked through a central (μ4-O) bridge. The Ce6Mn8 equals the highest nuclearity yet reported for a heterometallic Ce/Mn aggregate. In contrast to most of the previously reported heterometallic Ce/Mn systems, which contain only CeIV and either MnIV or MnIII, some of the aggregates presented here show mixed valency, either MnIV/MnIII (see 7) or CeIV/CeIII (see 4 and 5). Interestingly, some of the compounds, including the heterovalent CeIV/CeIII4, could be obtained from either CeIII(NO3)3⋅6 H2O or (NH4)2[CeIV(NO3)6] as starting material.
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