Nickel(II) and Palladium(II) Complexes Bearing an Unsymmetrical Pyrrole-Based PNN Pincer and Their Norbornene Polymerization Behaviors versus the Symmetrical NNN and PNP Pincers.

Unsymmetrical pincers have been shown to be better than the corresponding symmetrical pincers in several catalysis reactions. A new unsymmetrical PNN propincer, 2-(3,5-dimethylpyrazolylmethyl)-5-(diphenylphosphinomethyl)pyrrole (1), was synthesized from pyrrole through Mannich bases in a good yield. In addition, the new byproduct 2-(3,5-dimethylpyrazolylmethyl)-5-(dimethylaminomethyl)- N-(hydroxymethyl)pyrrole was also isolated. The reaction of 1 with [PdCl2 (PhCN)2 ] and Et3 N in toluene yielded [PdCl{C4 H2 N-2-(CH2 Me2 pz)-5-(CH2 PPh2 )-κ3 P,N,N}] (2). The analogous reaction between 1 and [NiCl2 (DME)] or NiX2 (X = Br, I) in the presence of NEt3 in acetonitrile afforded [NiX{C4 H2 N-2-(CH2 Me2 pz)-5-(CH2 PPh2 )-κ3 P,N,N}] (3; X = Cl, Br, I). All complexes were structurally characterized. The norbornene polymerization behaviors of the unsymmetrical pincer complexes 2 and 3 in the presence of MMAO or EtAlCl2 were compared with those of the symmetrical pincer complexes chloro[2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrolido]palladium(II) (NNN), chloro[2,5-bis(diphenylphosphinomethyl)pyrrolido]palladium(II), and chloro[2,5-bis(diphenylphosphinomethyl)pyrrolido]nickel(II) (PNP) at different temperatures. The PNN and NNN complexes exhibited far greater activity on the order of 107 g of PNB/mol/h, with quantitative yields in some cases, in comparison to the PNP pincer palladium and nickel complexes. This trend was also supported by the i Pr group substituted PNP nickel and palladium pincer complexes. These polymerization behaviors are explained using steric crowding around the metal atom with the support of NMR studies and suggested that the activity increases as the Npyrazole donor increases. Polymers were characterized by 1 H NMR, IR, TGA, and powder XRD methods.