The interionic structure in solution of a series of [LAu(μ‐H)2WCp2][BF4] ion pairs (L=N‐heterocyclic carbene, phosphine or phosphite) has been elucidated by means of heteronuclear NOE and diffusion NMR. Selective ion pairing based on specific metallocene‐anion interactions has been observed for all species. The ancillary ligand L plays only a minor role in dictating the availability of secondary ion pair structures, mainly owing to steric factors. DFT calculations have indicated that the tungstenocene fragment delocalizes most of the positive charge and acts as the preferential anion anchoring point. Even though the interaction is highly specific, ion association in CD2Cl2 is not enhanced and the typical aggregation behavior of linear Au(I) ion pairs is observed.

Zirconocene cations react with Cp2WH2 affording the bimetallic [Cp2Zr(μ–H)(μ-h1:h5–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...