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

Zirconocene cations react with Cp 2 WH 2 affording the bimetallic [Cp 2 Zr(μ-H)(μ-η 1 :η 5 -C 5 H 4 )WHCp] + bridging hydride 1 (Cp = cyclopentadienyl anion, C 5 H 5 − ) 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. PMe 3 , 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 1 H NMR chemical shift values of the hydride, which correlate linearly with computed Zr-H distances. Reactivity experiments with H 2 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. σ-Bond metathesis between zirconocene cations and Cp 2 WH 2 affords a bimetallic bridging hydride with an out of plane configuration and no M-M interaction. Small molecules react predominantly at the Zr-C bond in the absence of bimetallic cooperativity.