Lanthanide oxochalcogenido clusters.

Lanthanide chalcogenolates react with either TeO(2) in pyridine or py-SO(3) in THF to give oxychalcogenido clusters. The sulfido derivatives (THF)(8)Ln(8)S(2)O(2)(SePh)(16) (Ln = Ce, Nd) are isostructural with previously reported oxoselenido compounds, and must be prepared at low temperatures to avoid the introduction of Se into the sulfide position. Analogous telluride derivatives for the early lanthanides were not obtained, but reactions of in situ prepared Ln(TePh)(3) with elemental Te and TeO(2) gave a complicated heterocluster product, with tetrametallic polytelluride [(py)(7)Ln(4)(mu(4)-Te)(mu(2)-Te(2))(2)(mu-eta(2)-eta(2)-Te(2)Te(Ph)Te(2))(TePh)] co-crystallizing with the oxotellurido compound [(py)(5)Ln(3)(mu(3)-O)(mu(2)-Te(2))(3)(TePh)] (Ln = Ho, Er).

Oxoselenido clusters of the lanthanides: rational introduction of oxo ligands and near-IR emission from Nd(III).

Reactions of Ln(SePh)3 with SeO2 in THF give octanuclear oxoselenido clusters with the general formula (THF)8Ln8O2Se2(SePh)16 (Ln = Ce, Pr, Nd, Sm). In this isomorphous series, the eight Ln(III) ions are connected in the center by a pair of mu3-O2- ligands and mu5-Se2- ligands, with 14 bridging and two terminal selenolate ligands capping the cluster surface. Thermal decomposition at 700 degrees C of the Nd compound in vacuo led to the formation of a phase mixture of NdSe2, Nd2Se3, and Nd2O3.

Lanthanide clusters with internal Ln: fragmentation and the formation of dimers with bridging Se(2-) and Se2(2-) ligands.

Reactions of "LnI(x)(SePh)(3-x)" (Ln = Dy, Ho) with elemental S/Se give (THF)14Ln10S6(Se2)6I6. The compounds are composed of a Ln6S6 double cubane core, with two twisted "Ln2(SeSe)3" units condensed onto opposing rectangular sides of the Ln6S6 fragment. This deposition of Ln2Se6 totally encapsulates the two central Ln's with chalcogen atoms (four S and four Se atoms), excluding neutral THF donors or iodides from the two primary coordination spheres.

Heterometallic lanthanide group 12 metal iodides.

Neodymium tri-iodide reacts with Group 12 metal (M; M = Zn, Cd, Hg) iodides to form heterometallic compounds. These Lewis acidic M cleave Nd-I bonds to give either ionic ([(THF)(5)NdI(2)][MI(3)THF]; M = Zn, Cd) or charge-neutral [(THF)(5)NdI(micro(2)I)HgI(3)] compounds. Differences in structure are interpreted primarily in terms of M-L bond strengths, rather than Nd-L bond strengths.

Lanthanide-transition metal chalcogenido cluster materials.

[(THF)3Sm(SePh)2Zn(SePh)2]n decomposes to give a variety of products, including [(THF)8Sm4Se(SePh)8](2+)[Zn8Se(SePh)16](2-), an ionic cluster that can also be prepared in more than 60% yield by stoichiometric addition of Se to a mixture of Sm(SePh)3 and Zn(SePh)2. The isostructural Nd compound [(THF)8Nd4Se(SePh)8](2+)[Zn8Se(SePh)16](2-) was also prepared by the stoichiometric route to establish the viability of this cluster type with redox-inactive Ln. In addition, the salt [Yb(THF)6](3+)[Fe4Se4(SePh)4](3-) was isolated and structurally characterized.