Tweaking the bridge in metallocene Zr(IV)/W(IV) bimetallic hydrides

Zirconocene cations react with Cp₂WH₂ affording the bimetallic [Cp₂Zr(μ-H)(μ-η¹:η⁵-C₅H₄)WHCp]⁺ bridging hydride 1 (Cp = cyclopentadienyl anion, C₅H₅^-) via σ-bond metathesis. Complex 1 features an atypical out of plane Zr(μ-H)W moiety, where no intermetallic interaction is involved, and a fluxional core. Coordination geometry and bond distances of the bridging hydride interaction can be modulated upon reaction with Lewis bases and unsaturated substrates. PMe₃, P(p-tol)₃, 3,5-dimethylpyridine and THF bind to 1 and shift the hydride bridge on the coordination plane of Zr. Insertion of olefins and alkynes into the Zr-C bond of 1 leads instead to alkyl and vinyl species where the Zr and W coordination planes are perpendicular to each other. Such alterations of the Zr(μ-H)W arrangement are reflected in the average ¹H NMR chemical shift values of the hydride, which correlate linearly with computed Zr-H distances. Reactivity experiments with H₂ showed that the bridging hydride interaction prevents bimetallic cooperativity and that σ-bond metathesis between Zr-C and H-H bonds is the preferred pathway for all the investigated complexes.