Synthesis of Hetero-Binuclear Complexes from Bisgermavinylidene

Bisgermavinylidene [(Me3SiNPPh2)2CGe→GeC­(PPh2NSiMe3)2] (1) has been used as a source of unstable germavinylidene for the synthesis of a series of heterobinuclear complexes. The reaction of 1 with stoichiometric amounts of transition metal chlorides MCl2 (M = Mn, Fe) yielded [(Me3SiNPPh2)2(GeCl)­CMn­(μ-Cl)]2 (2) and [(Me3SiNPPh2)2(GeCl)­CFeCl] (3), respectively. Treatment of 1 with Me3SiN3 gave the [2 + 3] cycloaddition product [(Me3SiNPPh2)2CGeN­(SiMe3)­NN] (4). While similar reaction of 1 with (nBu)3SnN3 (nBu = n-butyl) and water-borane adduct H2O → B­(C6F5)3 afforded the 1,2-addition products [(Me3SiNPPh2)­{(nBu)3Sn}­CPPh2NSiMe3GeN3] (5) and [HC­(PPh2NSiMe3)2Ge­(OH)­B­(C6F5)3] (6), respectively. The results suggested that the germanium–carbon bond in germavinylidene is capable of forming addition reaction products. The X-ray structures of 2–6 have been determined.