Bulky Phenyl Modifications of the Silanide Ligand Si(SiMe 3 ) 3 – Synthesis and Reactivity

The synthesis and structural characterization of bulkier variations of the very common organometallic compound M Si(SiMe 3 ) 3 , namely M Si(SiMe 3 )(SiPh 3 ) 2 3 and M Si(SiPh 3 ) 3 [ M = Li ( 1 ), K ( 5 )] are presented, which can be synthesized via a step by step exchange of SiMe 3 groups by bulkier SiPh 3 groups. This synthetic route is high selective and is performed in good yields via the silanes Si(SiMe 3 ) 2 (SiPh 3 ) 2 ( 2 ) and Si(SiMe 3 )(SiPh 3 ) 3 ( 4 ). Additionally, the corresponding silanes HSi(SiMe 3 )(SiPh 3 ) 2 ( 6 H ) and HSi(SiPh 3 ) 3 ( 7 H ) are obtained via the reaction of 3 and 5 with aqueous HCl, respectively. Oxidation of 6 H with CCl 4 gives the chlorsilane Cl‐Si(SiMe 3 )(SiPh 3 ) 2 ( 6 Cl ). The bulkiest chlorsilane Cl–Si(SiPh 3 ) 3 ( 7 ) is obtained by the reaction of 5 with E Cl 2 ( E = Sn, Pb).