Reactions of [W2(η-C5H4R)2X4](R = Me or Pri, X = Cl or Br) with Lewis bases and synthesis of a complex containing a perpendicular bridging iminoacyl ligand

Abstract

The WW triply bonded dimers [W₂(η-C₅H₄R)₂X₄](X = Cl, R = Prⁱ1a or Me 1b; X = Br, R = Prⁱ2) readily undergo addition reactions with various Lewis bases to give the complexes [W₂(η-C₅H₄Me)₂Cl₂(µ-Cl)₂(dmpe)][dmpe = 1,2-bis(dimethylphosphino)ethane],*[W₂(η-C₅H₄R)₂Cl₂(µ-Cl)₂(CO)₂],*fac-[W(η-C₅H₄Prⁱ)Br₃(CO)₂],*[W₂(η-C₅H₄R)₂Cl₃(µ-Cl)(µ-σ:η²-Bu^tNC)(Bu^tNC)], [N(PPh₃)₂][W₂(η-C₅H₄R)₂Cl₄(µ-Cl)] and [W₂(η-C₅H₄R)₂Cl₃(µ-Cl)(µ-σ:η²-R′CN)](R′= Me, Et* or Ph; R = Prⁱ or Me). Treatment of the last compounds with HCl affords the µ-iminoacyl derivatives trans- and cis-[W₂(η-C₅H₄R)₂Cl₄(µ-Cl)(µ-R′CNH)].* The compounds labelled* have been crystallographically characterised.