Synthesis, Structure, and Characterization of N-Ligated Mo6S8L6 Cluster Complexes. Molecular Precursors to Chevrel Phases

Octahedral Molybdenum Cluster Cyanide Complexes with Selenide and Halide Ligands in the Cluster Core

“…[15] This synthesis demonstrates that in [16] However, we find that the reaction of Mo 6 Y 12 (Y ϭ Cl, Br) with Cs 2 Se 3 leads to amorphous products that are different from those from the reaction with Cs 2 S 3 . To discover the structure of these products, we have ''excised'' the cluster core by treating these solids with KCN in boiling water, and then letting the resultant solutions evaporate.…”

New model of the electronic structure of the [Mo6X8(CN)6]6− clusters (XS, Se) based on the study of electron density distribution in the inner part of the Mo6 polyhedron

“…We used two quantum chemical methods, an ab initio self-consistent field (SCF) method and a density functional theory (DFT) approach (B3LYP approximation [2]), to investigate the electronic structure of [Mo 6 X 8 (CN) 6 ] 6Ϫ (XAS, Se) and Mo 6 S 8 clusters. SCF calculations were performed with two basis sets for C, N, and S atoms: 3-21G and 6-31G.…”

“…The calculated one-electron energy levels diagrams for [Mo 6 S 8 (CN) 6 ] 6Ϫ are shown in Figure 1 and Table III 6 ] 6Ϫ and 72 in the case of Mo 6 S 8 ) correspond to the molecular orbitals, formed mainly by the inner shells' atomic orbitals (3d, 4s, and 4p, for Mo, 1s-2s, 2p, and 3s for S and 1s for N and C) and CN molecular orbitals 1 and 2. These molecular orbitals are symmetry-adapted linear combinations of the corresponding atomic or CN group [7] shows that there is good agreement concerning the nature of the nine MOs of the upper group.…”

“…This is close to the model of the cluster formed by neutral molybdenum and sulfur atoms and negatively charged CN groups with a general electron density shift from inside (Mo3 S) and outside (CN Ϫ 3 S) "spheres" to the intermediate sulfur "sphere." In addition, in Mo 6 S 8 (CN) 6 ] 6Ϫ and Mo 6 S 8 clusters, there are molecular orbitals of a 1g symmetry, with the electron density mainly concentrated inside the Mo 6 octahedron (Fig. 2).…”

“…[7]). Starting from this observation, we studied the electron density distribution in Mo 6 S 8 (CN) 6 ] 6Ϫ along some of the edges and planes of the polihedron. edges of the polyhedron; it is never Ͻ0.08 e/au 3 .…”