<jats:title>Abstract</jats:title><jats:p>Treatment of pyridine‐stabilized silylene complexes [(η<jats:sup>5</jats:sup>‐C<jats:sub>5</jats:sub>Me<jats:sub>4</jats:sub>R)(CO)<jats:sub>2</jats:sub>(H)WSiH(py)(Tsi)] (R=Me, Et; py=pyridine; Tsi=C(SiMe<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>) with an N‐heterocyclic carbene <jats:sup>Me</jats:sup>I<jats:sup><jats:italic>i</jats:italic></jats:sup>Pr (1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) caused deprotonation to afford anionic silylene complexes [(η<jats:sup>5</jats:sup>‐C<jats:sub>5</jats:sub>Me<jats:sub>4</jats:sub>R)(CO)<jats:sub>2</jats:sub>WSiH(Tsi)][H<jats:sup>Me</jats:sup>I<jats:sup><jats:italic>i</jats:italic></jats:sup>Pr] (R=Me (<jats:bold>1‐Me</jats:bold>); R=Et (<jats:bold>1‐Et</jats:bold>)). Subsequent oxidation of <jats:bold>1‐Me</jats:bold> and <jats:bold>1‐Et</jats:bold> with pyridine‐<jats:italic>N</jats:italic>‐oxide (1 equiv) gave anionic η<jats:sup>2</jats:sup>‐silaaldehydetungsten complexes [(η<jats:sup>5</jats:sup>‐C<jats:sub>5</jats:sub>Me<jats:sub>4</jats:sub>R)(CO)<jats:sub>2</jats:sub>W{η<jats:sup>2</jats:sup>‐OSiH(Tsi)}][H<jats:sup>Me</jats:sup>I<jats:sup><jats:italic>i</jats:italic></jats:sup>Pr] (R=Me (<jats:bold>2‐Me</jats:bold>); R=Et (<jats:bold>2‐Et</jats:bold>)). The formation of an unprecedented W‐Si‐O three‐membered ring was confirmed by X‐ray crystal structure analysis.</jats:p>