Abstract The syntheses of new stable bivalent germanium, tin and lead homoleptic species (ArO)2M: (ArO = 2,4,6-[(CH3)2NCH2]3C6H2O; M = Ge (1), Sn (2), Pb(3), Ge(OSO2CF3)2·C4H8O2 (4) and heteroleptic species M ( OAr ) [ N(SiMe 3 ) 2 ] ( M = Ge ( 5 ), Sn ( 6 )) are described. New organometallic heterocycles, stable metalla-imines and germathione (ArO)2M = X (X = NSiMe3, S) and metal(II)-transition metal complexes are obtained starting from 1 and 2.