Halogen and Sulfur Oxidation of Germanium and Tin Dications

Herein we present the oxidation of base-stabilized tetrelII dications [LM][OTf]2 [L = BIMEt3 = tris(1-ethyl-benzoimidazol-2-ylmethyl)amine and M = Ge, Sn] with PCl5, SeCl4, Br2, and I2 to access dicationic dihalides [LMX2][OTf]2. The addition of oxygen-rich donor molecules (picoline N-oxide, OPEt3) to dications [LM][OTf]2 yielded donor–acceptor complexes bearing a tetrel(II) dication adjacent to a pnictogen(V) moiety. The addition of elemental sulfur to [LGe][OTf]2 yielded [(LGeS)2][OTf]4 containing a dimeric tetracation.