The synthetic and structural chemistry of catalytically useful trialkylsilylium salts with weakly coordinating carborane anions, R 3 Si(CHB 11 X 11 ), has been extended to the heavier group 14 elements. Et 3 Ge(CHB 11 H 5 Br 5 ) was prepared from Et 3 GeH and trityl CHB 11 H 5 Br 6 -. Its X-ray crystal structure shows ion-like character very similar to its Si congener. The heavier element analogues, Et 3 E(CHB 11 H 5 Br 6 ) (E = Sn, Pb), were prepared by chloride ion abstraction from Et 3 SnCl and Et 3 PbCl, respectively, using Et 3 Si(CHB 11 H 5 Br 6 ). Their crystal structures differ from those of the four-coordinate lighter elements by adopting five-coordinate trigonal-bipyramidal stereochemistries, reflecting the periodic table transition of these elements from semi-metals to metals. The carborane anions are weak, bridging, axial ligands connecting trigonal Et 3 E þ cation-like moieties in polymeric chain structures. When the less coordinating CHB 11 Cl 11 -anion is used, excess germane competes with the carborane anion for coordination to Ge and a salt of the new hydride-bridged cation [Et 3 Ge-H-GeEt 3 ] þ can be isolated. It has a distinctive νGeHGe IR band at ca. 1740 cm -1 analogous to the 1875 cm -1 band of the [Et 3 Si-H-Si-Et 3 ] þ cation. Comparable chemistry is not observed for the Sn and Pb congeners.