Restraining Symmetry in the Formation of Small Polyoxomolybdates: Building Blocks of Unprecedented Topology Resulting From “Shrink‐Wrapping” [H₂Mo₁₆O₅₂]¹⁰⁻‐Type Clusters

Abstract

A mixed-valence polyoxomolybdate cluster [H2MoVI12MoV4O52]10− was isolated by a new “shrink-wrapping” approach to trap clusters that display low symmetry and nonspherical topology (see scheme; HMTAH=protonated hexamethylenetetraamine). The unprecedented cluster topology results from the restriction of the reorganization of the cluster framework to more symmetrical clusters, yet it reacts with electrophiles, such as FeII.