Heterodimetallic Chalcogen‐Bridged Cubane‐Type Clusters of Molybdenum and Tungsten Containing First‐Row Transition Metals

Abstract

Transition metal cluster chalcogenides with cubane‐type structures are relevant to our understanding of several industrial and biological catalytic processes. Recent advances in cluster chemistry owe much to the development of rational synthetic approaches, an aspect that is emphasised in this review which focuses on cuboidal clusters of molybdenum and tungsten (M) with M2M′2S4 and M3M′Q4 (Q = S, Se) central units that incorporate a first‐row transition metal atom (M′). Special attention has been paid to the non‐aqueous chemistry of these compounds. The structural features of these complexes are discussed in relation to their electronic structures within the framework of molecular orbital theory, spectroscopic, magnetic and electrochemical experimental data. Finally, the importance of these clusters in catalysis, nonlinear optics and in the formation of supramolecular adducts is discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

The Role of Solvent on the Mechanism of Proton Transfer to Hydride Complexes: The Case of the [W3PdS4H3(dmpe)3(CO)]+ Cubane Cluster

“…[10,11] These investigations revealed the role of the solvent and counterion in the kinetics and mechanism of the proton-transfer reaction. Thus, the protonation of the hydride cubane-type cluster [W 3 Q 4 H 3 A C H T U N G T R E N N U N G (dmpe) 3 ] + (Q = S, Se; dmpe = 1,2-bis(dimethylphosphanyl)ethane) with HX (X = Cl, Br) in CH 3 CN and CH 3 + halide complexes [Eq.…”

Unprecedented Stereoselective Synthesis of Catalytically Active Chiral Mo3CuS4 Clusters

“…[8] Such synthetic strategies have been illustrated in the preparation of the trinuclear [Mo 3 S 4 (dmpe) 3 Cl 3 ] + sulfido cluster (dmpe = 1,2-bis(dimethylphosphino)ethane), recently reported by us. [9] The specific coordination of the diphosphane ligand, with one phosphorus atom trans to the capping , respectively.…”

“…[8] However, no studies concerning their resolution or a strategy for their diastereoselective synthesis have been reported. So far, the catalytic performance of cuboidal Mo 3 CuS 4 species has never been studied.…”

Unprecedented Solvent‐Assisted Reactivity of Hydrido W3CuS4 Cubane Clusters: The Non‐Innocent Behaviour of the Cluster‐Core Unit

“…During the course of this work a very interesting and unexpected conversion of cluster [1] + into [2] 2 + was observed in CH 3 CN/H 2 O mixtures, with formation of the acetonitrile complex [2] 2 + from [1] + being promoted by water. From a qualitative point of view, this reaction can be considered a new example of a process driven by solvation of the released chloride, [33][34][35] and a detailed experimental and theoretical study has been carried out with the aim of elucidating the kinetic and mechanistic features of this process. These studies have revealed an active role of the cluster core on the reactivity of the heterometal site, which is unprecedented in the chemistry of these compounds and opens up new possibilities for a better understanding of certain aspects of the reactivity and catalytic properties of this kind of clusters.…”

“…There are several examples of inorganic and organic reactions in which a similar effect has been observed. [33][34][35] The free energy for transfer of this anion from acetonitrile to water is À10.1 kcal mol…”