Synthesis and study of [MMn_3O_x] complexes: The effects of redox-​inactive metals on cluster properties and reactivity

Abstract

Lewis acidic redox-inactive metal ions are known to affect processes such as electron transfer, hydrogen atom transfer, and oxygen atom transfer in metal oxo compds. A series of structurally related [MMn_3O_2] and [MMn_3O_4] complexes contg. redox-inactive metals of various charge (M = Na^+, Ca^2+, Sr^2+, Zn^2+, Y^3+, and Sc^3+) were prepd. and structurally characterized. These complexes were studied to probe the effects of varying the redox-inactive metals in isostructural complexes on different chem. transformations of the clusters. Cyclic voltammetry of the compds. showed that the redox potentials of the clusters are dependent upon the Lewis acidity of the incorporated redox-inactive metal. The rates of oxygen atom transfer from the clusters as well as hydrogen atom transfer to the clusters are also affected by the different redox-inactive metal ions.