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Our recent study on formal halide adducts of disilenes led to the investigation of the synthesis and properties of β-fluoro- and chlorodisilanides. The reaction of the functionalized neopentasilanes (Me 3 Si) 3 SiSiPh 2 NEt 2 and (Me 3 Si) 3 SiSiMe 2 OMe with KO  t  Bu in the presence of 18-crown-6 provided access to structurally related β-alkoxy- and amino-substituted disilanides. The obtained Et 2 NPh 2 Si(Me 3 Si) 2 SiK·18-crown-6 was converted to a magnesium silanide and further on to Et 2 NPh 2 Si(Me 3 Si) 2 Si-substituted ziroconocene and hafnocene chlorides. In addition, an example of a silanide containing both Et 2 NPh 2 Si and FPh 2 Si groups was prepared with moderate selectivity. Also, the analogous germanide Et 2 NPh 2 Si(Me 3 Si) 2 GeK·18-crown-6 could be obtained.

β-Amino- and Alkoxy-Substituted Disilanides