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Influence of thiopheneyl‐based twisted backbone on the properties of α‐diimine nickel catalysts in ethylene polymerization

Daohong Liao, Shabnam Behzadi, Changwen Hong, Chen Zou, Muhammad Qasim, Min Chen

2021Applied Organometallic Chemistry17 citationsDOI

Abstract

Abstract The modification of ligand sterics has become a prevalent strategy to tune the properties of α‐diimine‐type nickel catalysts. The majority of the works in this field focus on the modifications of the aniline moiety. In this contribution, we decide to explore the influence of backbone structures. Specifically, nickel complexes bearing 2,5‐dimethyl‐thien‐3‐yl and 2‐methyl‐5‐phenylthien‐3‐yl backbone structures were prepared and characterized. In comparison with the nickel analogue with methyl backbone, these new nickel complexes demonstrate much higher catalytic activity and thermal stability upto 80°C in ethylene polymerization and generate polymer products with much higher molecular weight along with lower branching density and higher melting points. It is believed that the bulky substituents at ligand backbone will exert influence on the N ‐aryl moieties and increase steric bulkiness around the metal center. This backbone strategy is applicable for future studies in other catalytic reactions.

Topics & Concepts

ChemistryDiimineSteric effectsMoietyBranching (polymer chemistry)CatalysisEthylenePolymer chemistryNickelLigand (biochemistry)PolymerizationAnilineArylPolymerPhotochemistryStereochemistryOrganic chemistryReceptorAlkylBiochemistryOrganometallic Complex Synthesis and CatalysisCatalytic Alkyne ReactionsCarbon dioxide utilization in catalysis
Influence of thiopheneyl‐based twisted backbone on the properties of α‐diimine nickel catalysts in ethylene polymerization | Litcius