Organosilicon hypersilylchalcogenolates and related compounds

Reaction of potassium hypersilylchalcogenolates (Me3Si)3SiEK (E = S, Se, Te) with organochlorosilanes R4 − xSiClx (R = Me, Ph; x = 1–4) and methylchlorodisilanes (Si2Me5Cl, 1,2-Si2Me4Cl2) yields organosilicon hypersilylchalcogenolates [(Me3Si)3SiE]xSiR4 − x (x = 1–4) and [(Me3Si)3SiE]xSi2Me6 − x (x = 1, 2). A partial substitution product, [(Me3Si)3SiSe]2SiPhCl (2) has been obtained by reaction of PhSiCl3 with 1.5 equivalents (Me3Si)3SiSeK. Besides characterization by 1H, 13C, 29Si, 77Se and 125Te NMR spectroscopy the compounds [(Me3Si)3SiTe]2SiPh2 (1), [(Me3Si)3SiSe]2SiPhCl (2) and [(Me3Si)3SiSe]2Si2Me4(3) have also been analyzed by crystal structure analyses. Starting from (Me3Si)5Si2K treatment with sulfur gave the highly branched potassium heptasilanylthiolate (Me3Si)5Si2SK. Reactions with methylchlorosilanes Me4 − xSiClx (x = 1, 2, 3) yielded organosilicon heptasilanylthiolates [(Me3Si)3Si–(Me3Si)2Si–S]xSiMe3 − x.