An important challenge in modern coordination chemistry is the construction of larger more complex materials from simple monometallic and bimetallic building blocks. The ability to control the assembly of such systems revolves around the ability to selectively access coordination sites around the metal. As such, complexes that are stabilized by weakly bound solvent molecules represent a useful precursor for building larger, more complex molecular architectures. Our group has been investigating the substitution and redox chemistry of the homoleptic dimolybdenum complex [Mo2(DMF)10]4+ which possesses a Mo-Mo quadruple bond supported solely by solvent. Unlike, the analogous acetonitrile complex, [Mo2(DMF)10]4+ reacts readily with dioxygen to produce [Mo2O4(DMF)6]2+ in good yield. This Mo(V)-Mo(V) oxo dimer can also be prepared by zinc reduction of the Mo(VI) precursor, MoO42-. Interestingly, these two bimetallic species, [Mo2(DMF)8]4+ and [Mo2O4(DMF)6]2+, will react with each other to form the triangular, Mo(IV)-Mo(IV)-Mo(IV) cluster, [Mo3O4(DMF)9]4+. This species consist of a Mo3O44+ core that adopts a partial cubane geometry which is supported by solvent. We are examining the substitution chemistry of these clusters in an effort to exploit these solvent supported coordination sites to link the complexes into larger, more complex clusters. Details of the synthesis, spectroscopy, electrochemistry, structure, and reactivity of these new solvated species will be presented.

Synthesis, characterization, and reactivity of small, solvent supported molybdenum clusters

251st National Meeting (2016)

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