Authors Das, S; Subramaniyan, V; Mani, G in AMER CHEMICAL SOC published article about VINYL POLYMERIZATION; CATALYTIC-ACTIVITY; ETHYLENE POLYMERIZATION; ADDITION POLYMERIZATION; NI COMPLEXES; LIGAND; PHOSPHINE; IRON; COORDINATION; PCN in [Das, Sanghamitra; Subramaniyan, Vasudevan; Mani, Ganesan] Indian Inst Technol Kharagpur, Dept Chem, Kharagpur 721302, W Bengal, India in 2019.0, Cited 104.0. HPLC of Formula: C5H8N2. The Name is 3,5-Dimethyl-1H-pyrazole. Through research, I have a further understanding and discovery of 67-51-6
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 Et3N in toluene yielded [PdCl-{C4H2N-2-(CH(2)Me(2)pz)-5-(CH2PPh2)-kappa P-3,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{C4H2N-2-(CH(2)Me(2)pz)-5-(CH2PPh2)-kappa P-3,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 10(7) 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 Pr-i 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 N-pyrazole donor increases. Polymers were characterized by H-1 NMR, IR, TGA, and powder XRD methods.
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Reference:
Pyrazole – Wikipedia,
,Pyrazoles – an overview | ScienceDirect Topics