The Coordination Chemistry and Clustering of Subvalent Ga+ and In+ upon Addition of σ-Donor Ligands

Abstract

This review addresses the coordination chemistry (mainly) enabled by using the univalent [M(fluoroarene)2–3]+[Al(ORF)4]−-salts (M=Ga, In; RF=C(CF3)3) as robust starting materials. In the course of this work, it became clear that the orbital energy of the ns2 (n=4, 5) lone pair in such [:M(L)n]+ cations reacts drastically depending on the quality of the ligand employed. Activation of the lone pair with strong σ-donor ligands might be used for bond activation and oxidative addition reactions. Yet, unexpectedly, using sterically undemanding and electron rich ligands with limited π-accepting properties, aggregation to highly charged and rather unusual univalent cluster cations [Mn(L)m]°+ (n=2…5, m=4…6, o=3…5) was observed. An overview and rationalization of these findings is presented here.