Chain‐walking polymerization of ethylene and 1‐octene with ortho ‐phenyl‐based α ‐diimine Ni (II) catalysts

A class of ortho ‐phenyl‐substituted Ni (II) α ‐diimine complexes with variable electronic nature in the 4‐phenyl position, {[(4‐Me‐2‐(4‐R‐C 6 H 4 )C 6 H 3 N=C) 2 Naphth]NiBr 2 , R = OMe ( C1 ); R = Me ( C2 ); R = H ( C3 )}, was prepared and characterized. These nickel dibromide complexes were confi...

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Veröffentlicht in:Applied organometallic chemistry 2023-11, Vol.37 (11)
Hauptverfasser: Wu, Jie, Li, Pei, Zhang, Juan, Dong, Zhengquan, Li, Wu, Bashir, Muhammad Sohail, Li, Yougui, Wang, Fuzhou
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Sprache:eng
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Zusammenfassung:A class of ortho ‐phenyl‐substituted Ni (II) α ‐diimine complexes with variable electronic nature in the 4‐phenyl position, {[(4‐Me‐2‐(4‐R‐C 6 H 4 )C 6 H 3 N=C) 2 Naphth]NiBr 2 , R = OMe ( C1 ); R = Me ( C2 ); R = H ( C3 )}, was prepared and characterized. These nickel dibromide complexes were confirmed by X‐ray crystallography analysis and crystallized as a centrosymmetric bromine‐bridged dimer in a distorted tetrahedral geometry at the two Ni (II) centers connected by a four‐membered ring. Because of the conjugation effect and steric hindrance effect of ortho ‐phenyl substituent, these Ni‐Et 2 AlCl systems via controlled chain‐walking ethylene polymerization performed with high catalytic activities of up to 3.10 × 10 6  g PE (mol Ni h) −1 to yield high molecular weight branched PEs with narrow M w / M n values (PDI ≤ 2.39). This Ni (II) system also conducted the chain‐walking polymerization of 1‐octene, resulting in highly branched polyolefins (up to 10 7 branches/1000C).
ISSN:0268-2605
1099-0739
DOI:10.1002/aoc.7246