Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory

摘要

Neutral phosphidozirconocene complexes Cp2Zr(PR2)Me (Cp=cyclopentadienyl; 1a: R=cyclohexyl (Cy); 1b: R=mesityl (Mes); 1c: R=tBu) undergo insertion into the Zr-P bond by non-enolisable carbonyl building blocks (O=CRR), such as benzophenone, aldehydes, paraformaldehyde or CO2, to give Cp2Zr(OCRRPR2)Me (3-7). Depending on the steric bulk around P, complexes 3-7 react with B(C6F5)(3) to give O-bridged cationic zirconocene dimers that display typical frustrated Lewis pair (FLP)/ambiphilic ligand behaviour. Thus, the reaction of {Cp2Zr(-OCHPhPCy2)MeB(C6F5)(3)}(2) (10a) with chalcone results in 1,4 addition of the Zr+/P FLP, whereas the reaction of {Cp2Zr(-OCHFcPCy(2))MeB(C6F5)(3)}(2) (11a; Fc=(C5H4)CpFe) with Pd((3)-C3H5)Cl(2) yields the unique Zr-Fe-Pd trimetallic complex 13a, which has been characterised by XRD analysis.