A Zirconium Complex Bearing an [NPN] Tridentate Ligand Composed of Dibenzophosphole and Pyrrolide Moieties: Synthesis, Structure, and Ethylene-Polymerization Ability

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2024-12-31 DOI:10.1021/acs.organomet.4c0039510.1021/acs.organomet.4c00395

Tomoyuki Toda*, Yuzuki Kasahara, Jin Iwasaki, Ayana Wakatsuki, Shun Ohta, Yoshihiro Matano and Katsuhiko Takenaka,

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引用次数: 0

Abstract

Post-metallocene catalysts constitute a remarkable class of homogeneous olefin polymerization catalysts owing to their exceptional activity and unique ability to copolymerize ethylene with α-olefins. The synthesis of Group 4 metal complexes, adorned with unprecedented ligand frameworks, has immense potential to yield polymerization performance surpassing that of conventional catalysts. In this field, soft/hard-mix-donor-type ligands have recently emerged as a focal point in the design of novel ligands for Group 4 transition metals. Thus, we herein synthesized an [NPN]-tridentate dianionic ligand containing dibenzophosphole and pyrrolides as a new type of soft/hard base mix-donor-type ligand and its zirconium complex, denoted as [NPN]Zr(NEt₂)₂. The [NPN] ligand and [NPN]Zr(NEt₂)₂ were comprehensively characterized by NMR and single-crystal X-ray crystal analysis. Ethylene homopolymerization was conducted under various conditions to determine the polymerization activity of [NPN]Zr(NEt₂)₂. In particular, ethylene polymerization was conducted at 0.1 MPa and 30 °C and catalyzed with [NPN]Zr(NEt₂)₂ with dried modified methylalumoxane as an activator, resulting in 7600 kg of (PE) mol(Zr)⁻¹ h^–1 MPa^–1 activity and linear PE with a high melting point. Overall, this study expands the repertoire of Group 4 metal catalysts, while underscoring their proficiency in tailoring advanced polymeric materials.

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.