New Aspects with Regard to Silanide Chemistry in Particular Formation and Structure of the First Disilyl Sodate [K(Me 2 SiO) 7 ][( t Bu 3 Si) 2 MeSi‐Na‐SiMe(Si t Bu 3 ) 2 ]

:The silanide Na[SiMe(Si t Bu 3 ) 2 ] was prepared by three step synthesis: In a first step, two equivalents of Na[Si t Bu 3 ] were reacted with Cl 2 MeSi‐H to give ( t Bu 3 Si) 2 MeSi–H. In a second step the silane ( t Bu 3 Si) 2 MeSi–H was brominated. Thereby we could isolate single crystals of ( t Bu 3 Si) 2 MeSi–Br (monoclinic, space group C 2/ c ), which were suitable for X‐ray diffraction. Subsequent reaction of ( t Bu 3 Si) 2 MeSi–Br with sodium yielded the silanide Na[SiMe(Si t Bu 3 ) 2 ] in heptane at room temperature. X‐ray quality crystals of the donor‐free silanide Na[SiMe(Si t Bu 3 ) 2 ] (monoclinic, space group P 2 1 / c ) were grown from heptane at room temperature. The 29 Si NMR spectrum of a 1:1 solution of K[O t Bu] and Na[SiMe(Si t Bu 3 ) 2 ] in thf revealed resonances, which could not be attributed either to Na[SiMe(Si t Bu 3 ) 2 ] nor K[SiMe(Si t Bu 3 ) 2 ]. Single crystals of [K(Me 2 SiO) 7 ][( t Bu 3 Si) 2 MeSi–Na–SiMe(Si t Bu 3 ) 2 ] were grown from an equimolar mixture of K[O t Bu] and Na[SiMe(Si t Bu 3 ) 2 ] in heptane over a period of 4 weeks at room temperature. The potassium disilylsodate was characterized by X‐ray crystallography (trigonal, space group P 3 1 21).