Organo‐Phosph(on/in)ate‐Bridged Dimers of Vanadium(IV) Complexes with the Kläui Ligand: Synthesis and Characterization

A series of dinuclear organophosphorus‐bridged vanadium(IV) complexes with the Kläui ligand, [CpP OMe Co] – , have been synthesized to model the catalytic activity of industrially used vanadium phosphate oxidation catalysts. Dimeric species of the general formula [(CpP OMe Co)V(O)(μ‐O 2 PR′R″)] 2 (R′,R″ = H, OH, Me, Ph, or 4‐OPh‐NO 2 ), [(CpP OMe Co)V(O)] 2 (μ‐oxalate), and [(CpP OMe Co)V(Cl)] 2 (μ‐oxalate) are reported. These complexes have been characterized via spectral and magnetic analyses. The synthesis, characterization, and X‐ray structures of the mononuclear vanadium(IV) complexes (CpP OMe Co)V(O)Cl(OH 2 ) and(CpP OMe Co)V(O)(acac) are also presented here. [CpP OMe Co] – = η 5 ‐cyclopentadienyltris(dimethylphosphito‐κ 1 P )cobaltate(III); acac = acetylacetonate.