Bis(germaamides) and their thio- and seleno- analogs are unknown. This work reports the isolation and characterization of the first examples of thio- and seleno-analogs of bis(germaamides) 7 and 8 containing two Ge(E)NR2 moieties (E = S, Se; R = SiMe3). These compounds were obtained by oxidizing the bulky pyrrole-imine dimeric ligand-stabilized bis(aminogermylene) 5 with elemental sulfur and selenium. This study also highlights the first ever application of the bulky pyrrole-imine dimeric ligand 3 to simultaneously stabilize two low valent centers (germylenes or stannylenes). Furthermore, the bonding in the thio- and seleno bis(germaamides) 7 and 8 was investigated in detail using single–crystal X-ray diffraction and DFT calculations.
