Self-Assembly of Magnesium Hydride Clusters Driven by Chameleon-Type Ligands

While magnesium hydride complexes are generally stabilized by hard, bulky N-donor ligands, softer ligands with a broad variety of coordination modes are shown to efficiently adapt themselves to the large variety of Mg²⁺ centers in a growing magnesium hydride cluster. A P,N-chelating ligand is introduced that displays coordination modes between that of enamide, aza-allyl, and phosphinomethanide. Slight changes in the ligand bite angle have dramatic consequences for the structure type. The hitherto largest neutral magnesium hydride clusters are isolated either in a nonanuclear sheet-structure (brucite-type) or a dodecanuclear ring structure.