The coordination chemistry of simple inorganic elemental clusters as well as cages is a long term research endeavour of our group. Complexes of known allotropes, metastable allotropes and hitherto unknown versions of an element were accessible. Also here, gas phase chemistry was an inspiration, as many of the clusters were initially observed by mass spectrometry. However, structure predictions were not necessarily correct...

However, also novel homo- and hetropolyatomic elemental cations were accessible. The routes to [P₉]⁺[Al(OR^F)₄]^–, the first phosphorus cation, and [P₃E]⁺[Al(OR^F)₄]^–, the first tetrahedral cation, are included in the next two figures.