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

Selwin FernandoMartina LandriniAlceo MacchioniDavid L HughesPeter H M BudzelaarLuca Rocchigiani
Published in: Dalton transactions (Cambridge, England : 2003) (2023)
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.
Keyphrases
  • pet imaging
  • ionic liquid
  • high resolution
  • magnetic resonance imaging
  • positron emission tomography
  • transition metal
  • mass spectrometry