A series of neutral and cationic germylene-bridged complexes and a neutral germyl(germylene) complex have been synthesized and characterized by NMR spectroscopy and X-ray crystallography. Reaction of 1 equiv of primary germanes, RGeH3 (R = Ph, Bu-t), with [RhIr(CO)(3)(dppm)(2)] (1) at low-temperature yields [RhIr(GeH2R)(H)(CO)(3)(dppm)(2)] (R = Ph (3) or Bu-t (4)), the products of single Ge-H bond activation, which upon warming transform to the germylene-bridged dihydrides, [RhIr(H)(2)(CO)(2)(mu-GeHR)(dppm)(2)] (R = Ph (5) or Bu-t (6)) by activation of a second Ge-H bond accompanied by CO loss. Both classes of compounds have the diphosphines folded back in a "cradle-shaped" geometry. Although compound S reacts with additional phenylgermane at -40 degrees C to give a germylene-bridged/germyl product, [RhIr(GeH2Ph)(H)(2)(CO)(2)(k(1)-dppm)(mu-GeHPh)(mu-H)(dppm)] (7), warming results in decomposition. However, reaction of 5 with 1 equiv of diphenylgermane at ambient temperature results in a novel mixed bis(mu-germylene) complex, [RhIr(CO)(2)(mu-GeHPh)(mu-GePh2)(dppm)(2)] (8), containing both mono- and disubstituted germylene fragments. Reaction of 1 equiv of diphenylgermane with complex 1 produces a similar monogermylene-bridged product, [RhIr(H)(2)(CO)(2)(mu-GePh2)(dPPm)(2)] (9), while reaction of 1 with 2 equiv of diphenylgermane yields the germyl/germylene product [RhIr(H)(GeHPh2)(CO)(3)(k(1)-dppm)(mu-GePh2)(dppm)] (10). The above reactions, incorporating first one and then a second equivalent of primary and secondary germanes, were studied by low-temperature multinuclear NMR spectroscopy, revealing details about the stepwise activations of multiple Ge-H bonds. Reaction of diphenylgermane with the cationic complex [RhIr(CH3)(CO)(2)(dppm)(2)][CF3SO3] (2) leads to a cationic A-frame-type germylene- and hydride-bridged product, [RhIr(CO)(2)(mu-H)(mu-GePh2)(dppm)(2)][CF3SO3] (3), which reversibly activates H-2, yielding a germyl-bridged dihydride and reacts stoichiometrically with water, methanol, and HCl to yield the respective germanol, germamethoxy, and germylchloride products.