Behavioral Patterns of Heterometallic Cuboidal Derivatives of [M₃Q₄(H₂O)₉]⁴⁺ (M = Mo, W; Q = S, Se)

Abstract

This Account reports recent progress in the study of some approximately 20 heterometal derivatives of [Mo3S4(H2O)9]4+ with reference also to W and Se analogues. Single cubes (3:1) and corner-shared double cubes (6:1), as well as dimers of the 3:1 single cubes, are considered. A classification of the heterometals as subtypes A, B, and C is introduced.

Cuboidal Mo3S4 and Mo3NiS4 Complexes Bearing Dithiophosphates and Chiral Carboxylate Ligands: Synthesis, Crystal Structure and Fluxionality

“…[7] The most extensively studied are the aqua complexes, for which the incorporation of more than 20 different heterometals has been achieved. [8] A serious drawback here is that a very high acidity has to be maintained to prevent hydrolysis (the water molecules coordinated to Mo cluster show high Brønsted acidity), which limits the scope of possible applications of these complexes. The cyclopentadienyl derivatives offer the possibility of completely blocking competing reactivity at Mo or W sites.…”

A New Series of Homologous Cluster Complexes [Mo3(M'EPh3)Q4Cl4(H2O)5] (M' = Ni, Pd; E = P, As, Sb; Q = S, Se)

“…[1] The bioinorganic significance of metal sulfide clusters is well known, and it has been put forward that the Mo 3 MЈS 4 (MЈ = Co, Ni) clusters in particular can constitute molecular models for the active sites of the industrial heterogeneous Co/MoS 2 or Ni/MoS 2 catalysts. [2] The Mo 3 PdS 4 4+ clusters catalyze nucleophilic addition to alkynes [3] and [Mo 3 NiS 4 (H 2 O) 10 ] 4+ has proved to be efficient in various heterogeneous catalytic processes. [4,5] Recently it was found that the heterometal in M 3 MЈS 4 4+ clusters (M = Mo, W; heterometal (MЈ) = Ni, Pd) stabilize very labile molecules of P(OH) 3 , RP(OH) 2 (R = H, Ph) and Ph 2 P(OH) by coordination at phosphorus [6][7][8] .…”

“…[9] A rational synthesis of these clusters is based on an addition of a heterometal in a low oxidation state (or even MЈ 0 ) to the trinuclear complexes with the M 3 Q 4 4+ cores. Especially productive are incorporations into the aqua complexes [M 3 Q 4 (H 2 O) 9 ] 4+ (M = Mo, W; Q = S, Se), [10] into the complexes with diphosphanes such as [M 3 Q 4 (dmpe) 3 -X 3 ] + , [9,11] were also studied and were used to follow the coordination of the solvent molecules at Mo sites and to assess relative strength of bonding in the clusters. Thermal properties were studied for 4 and 5.…”

Building Block Libraries and Structural Considerations in the Self-assembly of Polyoxometalate and Polyoxothiometalate Systems

“…The previously reported pseudocuboidal fragment [Mo3S4] 4+ tends to form low nuclearity clusters. It can react with transition metals or noble metal ions to form dimeric structures [48,49]. On the contrary, [Mo2O2S2] 2+ proved to be a lot more versatile and chemically suitable to interact constructively with a variety of organic and inorganic ligands including POM-based species [50].…”