The first characterized amidinate complexes of Ge have been prepared using alkylamidinates as ancillary ligands. Spectroscopic and structural characterization of the two complexes, (CyNC(Me)NCy)(2)Ge-II (1) and (CyNC(Bu-t)NCy)(2)Ge-II (2) (Cy = cyclohexyl), revealed that the Ge coordination geometry is distorted tetrahedral in which one of the vertices is occupied by a lone pair of electrons. Both 1 and 2 exhibited one bidentate and one monodentate (''dangling'') ligand. Rapid oxidative addition of chalcogen atom sources (styrene sulfide and Se) to these complexes resulted in a series of rare terminal chalcogenido complexes with the formulas (CyNC(R)NCy)(2)Ge=Ch [R = Me, Ch = S (3), Se(4); R = Bu-t, Ch = S (5), Se(6)]. The spectroscopic data and X-ray structure of 6 revealed a terminal Ge=Se complex; Mixed amidinato-amido analogues were similarly obtained. For example, [(CyNC(R)NCy)Ge-II[N(SiMe3)(2)] (R = Me, Bu-t) react to yield the corresponding terminal chalcogenido complexes. In the case of [(CyNC(Me)NCy)Ge-II[N(SiMe3)(2)]Se (10), a crystallographic study confirmed the presence of a terminal Ge=Se bond.