A series of 2-silyl- and 2-disilanyl-substituted 2-aryl-1,3-dithiane derivatives were prepared by the reactions of 2-aryl-2-lithio-1,3-dithianes with the corresponding chlorosilanes. Photolysis of 2-phenyl-2-(pentamethyldisilanyl)-1,3-di resulted in the intermediary formation of 1,1-dimethyl-2-phenyl-2-(trimethylsilyl)-1-silaethene.