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)

Abstract

The first monomeric germanethiocarbamyl halides containing a chelating β-diiminate ligand, L 2 (Cl)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 Å ( 2 ); Ge−Se = 2.21 Å ( 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 )).