Syntheses, structures and properties of [{HC(CMeNAr)2}Ge(E)X](Ar = 2,6-iPr2C6H3; E = S, Se; X = F, Cl)

For the first time the structurally characterized heavier chalcogen analogues of alkanoyl halides, [{HC(CMeNAr) 2}Ge(S)X](Ar = 2,6-iPr2C6H3; X = Cl (1), F (2)) and [{HC(CMeNAr)2}Ge(Se)X](X = Cl (4), F (5)) have been prepared from the starting material [{HC(CMeNAr)2}GeCl](3). The nature of the germanium–chalcogen bond is best described as between the two resonance structures, Ge+–E– GeE. The investigation of the reactivity of the germanium–halogen bond with RLi reagents (R = Me, nBu) led to the formation of [{HC(CMeNAr)2}Ge(E)R](E = S, R = Me (6); E = Se, R = Me (7), nBu (8)). The solid-state structures of 1, 2, 4, 5, 6, and 8 are reported.