Atomically precise expansion of unsaturated silicon clusters

Small‐ to medium‐sized clusters occur in various areas of chemistry, e.g. as active species of heterogeneous catalysis or transient intermediates during chemical vapor deposition. The manipulation of stable representatives is mostly limited to the stabilizing ligand periphery, virtually excluding the systematic variation of the property‐determining cluster scaffold. We now report the deliberate expansion of a stable unsaturated silicon cluster from six to seven and finally eight vertices. The consecutive application of lithium/naphthalene as reducing agent and decamethylsilicocene as electrophilic source of silicon results in the expansion of the core by precisely one atom with the potential of infinite repetition.

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