Description:
<jats:title>Abstract</jats:title><jats:p>In this contribution, a convenient synthetic method to obtain tris(trimethoxysilyl)silanides (M=Li, Na, K, Cu) <jats:bold>5 a</jats:bold>–<jats:bold>d</jats:bold> is described. <jats:bold>5 a</jats:bold>–<jats:bold>d</jats:bold> are easily accessible deriving from dodecamethoxyneopantasilane <jats:bold>4</jats:bold> in excellent yields and could be fully characterized <jats:italic>via</jats:italic> NMR spectroscopy and X‐ray crystallography. The efficiency of <jats:bold>5 a</jats:bold>–<jats:bold>d</jats:bold> to serve as a new building block in silicon chemistry is demonstrated by the reactions with two different types of electrophiles (carbon‐ and silicon‐electrophiles). In all cases the salt metathesis reaction gave rise to novel polysilanes in excellent yields. The possibility of a post‐functionalization to perhydropolysilanes as well as perchloropolysilanes enables the synthesis of new precursors for silicon deposition.</jats:p>