Intramolecularly‐stabilized germanium, tin, and lead alkoxides of the type M(OCH₂CH₂NR₂)₂ [R = Et, M = Ge (1); R = Me, M = Sn (2); R = Me, M = Pb (3)] are suitable precursors for the synthesis of group 14 chalcogenides ME (M = Ge, Sn, Pb; E = S, Se, Te) in scrambling reactions with (Me₃Si)₂S and (Et₃Si)₂E (E = Se, Te) at moderate temperatures via hot injection method. The reactions proceed with elimination of the corresponding silylether as was proven by in situ ¹H NMR spectroscopy. The solid‐state structures of the homoleptic complex 1 and the heteroleptic complex ClGe(OC₂H₄NEt₂) (4) were determined by single‐crystal X‐ray diffraction, whereas the group 14 chalcogenides were characterized by XRD, SEM, and EDX.

Dedicated to Prof. G. Schmid on the occasion of his 80th birthday.