From oxide to a new type of molecular tungsten compound: formation of bitetrahedral cluster complexes [{W₆(μ₄-O)₂(μ₃-CCN)₄}(CN)₁₆]¹⁰⁻ and [{W₆(μ₄-O)₂(μ₃-As)₄}(CN)₁₆]¹⁰⁻

Abstract

Two new mixed-valence tungsten cluster anions with bitetrahedral cores, {W6(μ4-O)2(μ3-CCN)4} and {W6(μ4-O)2(μ3-As)4} were synthesized from WO3.

PO23– and AsO3–: Pnictogenide Ligands in the Highly Charged Re4 Cluster Anions [{Re4(PO)3(PO2)}(CN)12]8–, [{Re4As2(AsO)2}(CN)12]8–, and [{Re4(AsO)4}(CN)12]8–

“…Examples of the ability of KCN to do this include the formation of unique Re 12 chalcocyanide cluster complexes obtained from ReS 2 and KCN, 32 as well as the original bitetrahedral tungsten cluster complexes that were recently reported. 33 The reactions of ReI 3 with KCN/NaCN and either arsenic or phosphorus that we report here resulted in compounds 1 and 2, which have the quite typical tetrahedral (Re 4 ) clusters for rhenium metal, and they are coordinated by the very unusual (PO 3− or As 3− ) or even unknown (PO 2 3− and AsO 3− ) μ 3 -ligands. Compound 2 was also obtained, when the starting arsenic reagent was As 2 O 3 instead of As.…”

“…In addition, KCN may also stabilize unusual cluster units. Examples of the ability of KCN to do this include the formation of unique Re 12 chalcocyanide cluster complexes obtained from ReS 2 and KCN, as well as the original bitetrahedral tungsten cluster complexes that were recently reported …”

From polygons to polyhedra through intermediate structures. A shape measures study of six-atom inorganic rings and clusters

“…However, a handful of structures appear as fused tetrahedra or with intermediate shapes in the way to the octahedron (between 24 and 70% octahedral). Three structures [130][131][132] from different spots of the path are shown in Fig. 25, together with their shape coordinates and some geometrical parameters for comparison.…”

The {Re4} Tetrahedral Cyanometalate Cluster Anion [{Re4(μ3-CCN)4}(CN)12]8– with Inner (μ3-CCN)3– Ligands and Its Features in Coordination of Cu2+ Cations

“…A characteristic feature of these reactions is their occurrence above the melting points of the corresponding cyanides. We have shown that this approach allows one to obtain compounds with new types of metal cores and/or unusual inner ligands, such as the {W 6 } bitetrahedron with μ 3 -CCN 3– ligands or the {Re 4 } tetrahedron with μ 3 -PO 2 3– and μ 3 -AsO 3– ligands …”