Reactivity of the pyridyl-1-azaallyl germanium(I) dimer LGeGeL (2; L = N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)) has been investigated. Treatment of germanium(I) dimer 2 with 1 equiv of azobenzene afforded the pyridyl-1-azaallyl digermahydrazine derivative [LGeNPh]2 (3). The reaction of 2 with 1 and 2 equiv of diiron nonacarbonyl, Fe 2(CO)9, afforded the novel unsymmetric germanium(I) complex [LGeGe(Fe(CO)4)L] (4) and the diiron Lewis acid-base adduct [LGe(Fe(CO)4)]2 (5). The solid-state structure of 4 reveals that the two germanium(I) centers within the same molecule have different coordinating geometries. Compound 4 can also be prepared by the facile reaction of the pyridyl-1-azaallyl germanium(II) chloride LGeCl (1) with Collman's reagent, Na2Fe(CO)4.