Phenylsilyl Chalcogenides, (Phenylsilyl)amines and Related Phosphonium (Phenylsilyl)methylides

The synthesis of 1,3‐diphenyldisiloxane ( 1 ) by hydrolysis of chloro(phenyl)silane is optimized, 1,3‐diphenyldisilthiane ( 2 ) is made available by the reaction of H 2 S with PhH 2 SiCl and triethylamine. 1,3‐Diphenyldisilselenane ( 3 ) is prepared from K 2 Se and PhH 2 SiBr. Selective ammonolysis of PhH 2 SiBr leads either to bis(phenylsilyl)amine ( 4 ) or to tris(phenylsilyl)amine ( 5 ). (Phenylsilyl)bis(trimethylsilyl)amine ( 6 ) is prepared by the reaction of 1,1,1,3,3,3‐hexamethyldisilazane with chloro(phenyl)silane and triethylamine. According to a crystal structure determination the molecule of 6 features a planar Si 3 N skeleton. Phenylsilylated phosphonium methylides are available by two synthetic pathways: Transsilylation of phosphonium (trimethylsilyl)methylides and direct silylation of unsubstituted phosphonium methylides R 3 P = CH 2 . The structure of the molecule Me 3 P = C(SiH 2 Ph) 2 ( 11 ) in the crystal also exhibits a virtually planar PCSi 2 skeleton, isoelectronic with Si 3 N.