Abstract

The reaction of sodium hydro‐tris(phenylthioimidazolyl)borate (NaTmPh) with silicon tetraiodide gives rise to the first crystallographically characterised molecular silicon compounds, [Si(TmPh)2] 2X (X = I– and I3–), in which the silicon is found in a regular S6 environment. The [Si(TmPh)2]2+ cation is subjected to analysis using DFT methods to explain why an S6 coordination motif is preferred to an S4 coordination motif.

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