The Coordination Chemistry and Clustering of Subvalent Ga+ and In+ upon Addition of σ‐Donor Ligands. Issue 18 (12th June 2021) - Dabringhaus, Philipp
Abstract: This review addresses the coordination chemistry (mainly) enabled by using the univalent [M(fluoroarene)2–3 ] + [Al(OR F )4 ] − ‐salts (M=Ga, In; R F =C(CF3 )3 ) as robust starting materials. In the course of this work, it became clear that the orbital energy of the n s 2 (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. Abstract :