The chemistry of beta-diketiminate germanium alkoxide complexes has been examined and shown to be in sharp contrast to its heavier congeners. For instance, (BDI)GeOR (BDI = [{N(2,6-(Pr2C6H3)-Pr-i)C(Me)}(2)CH], R = Pr-i, Bu-s, Bu-t) does not react with carbon dioxide to form a metal carbonate complex. Addition of aliphatic electrophiles, such as methyl iodide or methyl triflate, results in the net oxidative addition to the germanium, giving cationic tetravalent germanium complexes, complexes, (BDI)Ge(Me)OR][X] (X = I, OTf). An examination of the contrasting reactivities of the alkoxide ligand and the germanium loan pair with Lewis acids yielded the unusual germanium(II)-copper(I) adduct, {mu(2)-Cu2I2}-[(BDI)GeO'Bu](2). This complex not only displays a rare example of a divalent Ge-Cu bond, but is the first example in which a planar Cu2I2 diamond core possesses a three-coordinate copper bound to another metal center.