New Bimetallics of Mo and W with Metallocene, Metal Carbonyl and Bridging PPh$_{2}$ or ‘Cp’PPh$_{2}$ Units

Abstract

Ring substituted (R=$^{t}$Bu, SiMe$_{3}$) metallocene dichlorides undergo a nucleophilic substitution on one of the two rings upon the action of LiPPh$_{2}$M'(CO)$_{x}$ salts with the formation of chloro-hydrido complexes C$_{5}$H$_{3}$(R)PPh$_{2}$M'(CO)$_{x}$(C$_{5}$H$_{4}$R)M(H)Cl. Their UV irradiation leads to the chloro-bridged M(μ-Cl)M' separable diastereoisomers. Use of the ansa-metallocene dichlorides Me$_{2}$X(C$_{5}$H$_{4}$)$_{2}$MCl$_{2}$ (X=Si or C) allowed the access to the new bridging system M(μ-PPh$_{2}$, μ-Cl)M' (M=Mo, W ; M'=W).