Desirable multi-electron transformations of small molecule substrates can be catalyzed by metalloenzymes and metal surfaces through the cooperative chemistry of multiple metal centers. Trinuclear systems of divalent first row transition metals have been synthesized in Betley group to study the implications of metal-metal bonding on cluster reactivity. A hexadentate amido ligand framework is utilized to support an intermediate to high spin configuration of the metal core. This enhances the reactivity of these clusters resulting in group transfer from inorganic azide and thiocyanate to form �3- nitrido, and sulfido complexes. Reduction and oxidation of the corresponding adducts can afford several isolable oxidation states. The trinuclear nitride complexes can engage in facile carbon monoxide capture to yield cyanate adducts that are competent for further chemistry. Furthermore, exchange of the bound nitride to produce the trinuclear sulfide adduct is observed upon exposure of the nitride species to carbon disulfide. In addition to an overview of the reactivity of these �3 adducts with small molecules such as CO and CS2, the effects of metal identity, oxidation state of the metal core and identity of the atomic adduct on overall cluster reactivity will be discussed.

Reactivity of �<sup>3</sup>-atomic adducts of trinuclear complexes with small molecules

248th National Meeting (2014)

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Reactivity of �3-atomic adducts of trinuclear complexes with small molecules

Reactivity of �³-atomic adducts of trinuclear complexes with small molecules