Heteronuclear multiple bonding between heavier group 14 and 16 elements.: A new class of germylated compounds, the germanethiocarbamyl and germaneselenocarbamyl chlorides L2(Cl)GeY (Y = S, Se)

The first monomeric germanethiocarbamyl halides containing a chelating beta-diiminate ligand, L-2(CI)Ge=Y (L-2 = PhNC(Me)CHC(Me)NPh; Y = S (2), Y = Se (3)), have been prepared by the reaction of the corresponding heteroleptic halogermylene L-2(Cl)Ge (1) with elemental sulfur or black selenium in refluxing toluene. Single-crystal X-ray structural analyses of 2 and 3 reveal that the germanium centers reside in highly distorted tetrahedral environments in these compounds; short Ge-Y distances (Ge-S = 2.07 Angstrom (2); Ge-Se = 2.21 Angstrom (3)) are indicative of an unsaturated character of these germanium-chalcogen bonds. Selective reactions between 2 or 3 and MeLi afforded the corresponding alkylated germanechalcogenones L-2(Me)Ge=Y (Y = S (4), Se (5)).