Dinuclear Manganese and Cobalt Complexes with Cyclic Polyoxovanadate Ligands: Synthesis and Characterization of [Mn₂V₁₀O₃₀]^6– and [Co₂(H₂O)₂V₁₀O₃₀]^6–

Abstract

An all-inorganic complex, [Mn 2 {(VO 3 ) 5 } 2 ]6-(1), was synthesized, and the structure determination reveals a dinuclear manganese complex coordinated by two cyclic pentavanadate ligands. The cyclic pentavanadate units sandwich the edge-sharing octahedral dimanganese core through coordination of the oxido group of the pentavanadate. A dinuclear cobalt complex with a cyclic decavanadate, [Co 2 (OH 2 ) 2 -(VO 3 ) 10 ] 6-(2), was also synthesized. The structure analysis reveals a dinuclear cobalt complex with a macrocyclic decavanadate, which is composed of 10 VO 4 units joined by the vertex sharings. The CoO 6 octahedrons are edge-shared, with each cobalt octahedron coordinated to five oxido groups from the decavanadate. The remaining site is occupied by

Yttrium‐Containing Sandwich‐, Ring‐, and Cage‐Type Polyoxovanadates: Synthesis and Characterization

“…Thus, in these types of complexes, IR spectra give strong structural identification, based on the type of polyoxovanadate rings. Single crystals of (Et 4 N) 5 [Y(V 4 O 12 ) 2 ](1′), suitable for X-ray diffraction analysis, were obtained from the pyridine solution. Contrary to our assumption that only a peak from [Y{V 4 O 12 } 2 ] 5-({(Et 4 N) 6 Figure S2).…”

“…By using hydrated Y(NO 3 ) 3 , instead of Y(NO 3 ) 3 ·3DMSO, for the synthesis of 1, another crystal of (Et 4 N) 5 acts as a bidentate ligand through oxygen atoms coordinated to the Y 3+ center. However, the difficulty of adjusting the exact amount of water prevents satisfactory reproducibility of the synthesis of 1′′.…”

“…[2] To establish structure-control of rare-earth-containing polyoxometalates, for a rational synthesis, it is important to investigate the reaction conditions in terms of stoichiometry between the rare-earth cations and the polyoxometalates. [5,6] The number of VO 4 units and the structures of the circular polyoxovanadate frameworks are free to change until they occupy the available coordination sites on the heterometallic cores. Compound 3 possesses a cubane-type tetranuclear yttrium core, [Y 4 (OH) 4 ] 8+ , wrapped by a polyoxovanadate framework.…”

“…To achieve this goal, an yttrium cation is a good probe for rare-cess amount of pyridine drives the formation of 1, while in the presence of water or {Et 4 N}[VO 3 ], the formation of 2 is preferable. [5] In addition, the stabilization of rare-earth cations is also investigated by using polyoxovanadate rings. The spherical polyoxovanadate framework of 3 exhibits new types of inorganic coordination ligands and can include a cubane unit in the framework.…”

Structural conversion from bowl- to ball-type polyoxovanadates: Synthesis of a spherical tetradecavanadate through a chloride-incorporated bowl-type dodecavanadate

“…Inorganic complexes between a crown-type polyoxovanadate, (VO 3 ) n n-, and a transition metal cation produced a type of inorganic coordination complexes with a vanadium ring size of 4 < n < 10, depending on the type of metal cation used as a template [27][28][29][30]. To elucidate the reactivity of all-inorganic coordination complexes, a template-removal reaction was developed using the copper complex, …”