σ‑Silane, Disilanyl, and [W(μ‑H)Si(μ‑H)W] Bridging Silylene Complexes via the Reactions of W(PMe₃)₄(η²‑CH₂PMe₂)H with Phenylsilanes

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.