Preparation and Properties of Cp₂Zr(μ-NCAr₂)₂PdCl(Me), New Zr/Pd Heterobimetallic Complexes with Bridging Alkylideneamido Ligands

Zr/Pd heterobimetallic complexes with bridging alkylideneamido ligands, Cp2Zr(μ-NCAr2)2PdCl(Me) (Ar = Ph, C6H4Me-4), were prepared from the reaction of Cp2Zr(NCAr2)2 with PdCl(Me)(cod) (cod = 1,5-cyclooctadiene). Cp2Zr(μ-NCAr2)2PdCl(Me) complexes have puckered ZrN2Pd rings with Zr−Pd distances of 2.8135(5) Å (Ar = Ph) and 2.8416(4) Å (Ar = C6H4Me-4), respectively. The complexes reacted with HCl to afford trans-PdCl(Me)(NHCAr2)2 and Cp2ZrCl2. Exposure of a CH2Cl2 solution of trans-PdCl(Me){NHC(C6H4Me-4)2}2 to light results in the formation of a mixture of cis- and trans-PdCl(CHCl2){NHC(C6H4Me-4)2}2.