Hexasilylbenzene, C 6 (SiH 3 ) 6

The title compound was obtained in a four‐step synthesis starting from (4‐methoxyphenyl)silane. Owing to the presence of activating p ‐methoxy groups in the key intermediate hexakis[(4‐methoxyphenyl)silyl]benzene ( 4 ), the peripheral aryl groups can be cleaved selectively from the silicon atoms with trifluoromethanesulfonic acid, leaving the Si–C bonds to the central benzene ring intact. LiAlH 4 reduction of the resulting hexakis[(trifluoromethylsulfonyloxy)silyl]benzene ( 5 ) finally leads to crystalline, sublimable, air‐stable C 6 (SiH 3 ) 6 ( 6 ), m.p. 165°C. In the crystals (triclinic, space group P &1macr;) the structure of the centrosymmetrical molecules approaches very closely point group D 3d , as predicted from theoretical considerations.