Halogen and Sulfur Oxidation of Germanium and Tin Dications.

Herein we present the oxidation of base-stabilized tetrel dications [LM][OTf] [L = BIMEt = tris(1-ethyl-benzoimidazol-2-ylmethyl)amine and M = Ge, Sn] with PCl, SeCl, Br, and I to access dicationic dihalides [LMX][OTf]. The addition of oxygen-rich donor molecules (picoline N-oxide, OPEt) to dications [LM][OTf] yielded donor-acceptor complexes bearing a tetrel(II) dication adjacent to a pnictogen(V) moiety. The addition of elemental sulfur to [LGe][OTf] yielded [(LGeS)][OTf] containing a dimeric tetracation.