Abstract
A mononuclear complex [MoOCl4(H2O)]− readily forms a metal−metal bonded {Mo2O4}2+ core. A high content of pyridine in the reaction mixture prevents further aggregation of dinuclear cores into larger clusters and a neutral, dinuclear complex with the [Mo2O4Cl2(Py)4] composition is isolated as a product. Solid state structures of two compounds containing this complex, [Mo2O4Cl2(Py)4]·2.25Py (1) and [Mo2O4Cl2(Py)4]·1.5PyHCl (2), were investigated by X-ray crystallography.
Highlights
The {Mo2O4}2+ core with d electrons localized in a Mo(V)−Mo(V) single bond appears as a recurrent structural motif in many contexts of molybdenum(V) coordination chemistry [1,2,3,4,5,6,7]
The aggregation of dinuclear units is made possible by the ability of oxide and alkoxide ions to participate in μ2, μ3- or even μ4-bridging interactions
Changes in the contents of reaction mixtures or reaction conditions resulted in clusters with different nuclearities or different connectivities among the dinuclear building blocks
Summary
The {Mo2O4}2+ core (shown in Scheme 1) with d electrons localized in a Mo(V)−Mo(V) single bond appears as a recurrent structural motif in many contexts of molybdenum(V) coordination chemistry [1,2,3,4,5,6,7]. A group of high-nuclearity oxomolybdenum(V) complexes whose structures may be seen as the assemblies of two or more {Mo2O4}2+ units has emerged in the past two decades [8]. The aggregation of dinuclear units is made possible by the ability of oxide and alkoxide ions to participate in μ2-, μ3- or even μ4-bridging interactions. Three, four or up to six dinuclear units were linked through bridging oxides and/or methoxides to form tetranuclear, hexanuclear, octanuclear, decanuclear and dodecanuclear clusters with the [Mo4O8(OMe)2Cl2(Py)4],. The possible role that methanol or alcohols in general play in the formation of dinuclear units and their further aggregation will be discussed presently. In the absence of alcohol, (PyH)5[MoOCl4(H2O)]3Cl2 produced in the mixture of pyridine and a non-coordinating solvent two compounds which both contained a dinuclear {Mo2O4}2+based complex with the [Mo2O4Cl2(Py)4] composition.
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