σ‑Silane, Disilanyl, and [W(μ‑H)Si(μ‑H)W] Bridging Silylene Complexes <i>via</i> the Reactions of W(PMe<sub>3</sub>)<sub>4</sub>(η<sup>2</sup>‑CH<sub>2</sub>PMe<sub>2</sub>)H with Phenylsilanes
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W(PMe3)4(η2-CH2PMe2)H reacts with PhSiH3 to give the first examples of diphenyldisilanyl compounds, W(PMe3)4(SiH2SiHPh2)H3 and W(PMe3)3(SiH2Ph)(SiH2SiHPh2)H4, via a mechanism that is proposed to involve migration of a SiHPh2 group to a silylene ligand. In addition to the formation of the aforementioned mononuclear compounds, the reaction of W(PMe3)4(η2-CH2PMe2)H with PhSiH3 also yields a novel dinuclear compound, [W(PMe3)2(SiHPh2)H2](μ‑Si,P-SiHPhCH2PMe2)(μ‑SiH2)[W(PMe3)3H2], which features a bridging silylene ligand that participates in 3-center-2-electron interactions with both tungsten centers. The bonding within the [W(μ‑H)Si(μ‑H)W] core can be described by a variety of resonance structures, some of which possess multiple bond character between tungsten and silicon. In this regard, [W(PMe3)2(SiHPh2)H2](μ‑Si,P-SiHPhCH2PMe2)(μ‑SiH2)[W(PMe3)3H2] possesses the shortest W–Si bond length reported. The corresponding reaction of W(PMe3)4(η2-CH2PMe2)H with Ph2SiH2 yields the σ-silane compound, W(PMe3)3(σ-HSiHPh2)H4.
