Coplanar binuclear group 4 post-metallocene complexes supported by chelating μ-(σ-aryl) ligands: characterisation and olefin polymerisation catalysis

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 53; no. 1; pp. 346 - 353
• Main Authors: Li, Yufang, Liu, Qian, Bao, Junhui, Yiu, Shek-Man, Chan, Michael C. W
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 19.12.2023
• Subjects: Aromatic compounds; Bimetals; Binding sites; Catalysis; Catalysts; Chelation; Congeners; Crystallography; Ethylene; Hydrogen atoms; NMR spectroscopy; Para hydrogen; Polymerization; Substrates; Zirconium
• ISSN: 1477-9226; 1477-9234; 1477-9234
• DOI: 10.1039/d3dt03641c

The report concerns expansion of the previously developed M-[O,N,C] [pyridine-2-phenolate-6-(σ-aryl)] catalyst system into rigid, coplanar bimetallic assemblies, which afford metal-metal distances that are predetermined yet amenable for cooperativity, as well as locked-in " syn " orientation of binding sites that offer the same direction of access for substrates. The binuclear complexes are generated in a regioselective manner to yield para hydrogen atoms (not ortho ) at the central μ-aryl moiety, and have been characterised by multinuclear NMR spectroscopy. The " anti " (showing opposite directions of access) and mononuclear analogues have also been prepared for comparison purposes. Six syn -type bimetallic derivatives of Ti, Zr and Hf have been characterised by X-ray crystallography, to reveal metal-metal separations of 6.3-6.7 Å. For ethylene and ethylene/1-octene polymerisation reactions in conjunction with trityl borate, the syn -Ti 2 catalysts display superior efficiencies and produced polymers with higher M w values than for the anti and mono-Ti congeners, thus indicating the possibility of favourable enchainment interactions and cooperative reactivity. Rigid binuclear assemblies with M M distances and syn binding sites that are amenable for cooperative reactivity have been structurally characterised; the Ti 2 catalysts are more active than anti and mono-Ti controls and produced higher- M w polymers.