Lanthanide Complexes Supported by a Trizinc Crown Ether as Catalysts for Alternating Copolymerization of Epoxide and CO2: Telomerization Controlled by Carboxylate Anions

被引：89

作者：

Nagae, Haruki ^{[1
]}

Aoki, Ryota ^{[1
]}

Akutagawa, Shin-nosuke ^{[1
]}

Kleemann, Julian ^{[2
]}

Tagawa, Risa ^{[1
]}

Schindler, Tobias ^{[2
]}

Choi, Gyeongshin ^{[1
]}

Spaniol, Thomas P. ^{[2
]}

Tsurugi, Hayato ^{[1
]}

Okuda, Jun ^{[2
]}

Mashima, Kazushi ^{[1
]}

机构：

[1] Osaka Univ, Grad Sch Engn Sci, Dept Chem, Toyonaka, Osaka 5608531, Japan

[2] Rhein Westfal TH Aachen, Inst Inorgan Chem, Landoltweg 1, D-52062 Aachen, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 09期

关键词：

copolymerization; lanthanides; macrocycles; telomerization; zinc; EARTH TERNARY CATALYST; CARBON-DIOXIDE; CYCLOHEXENE OXIDE; PROPYLENE-OXIDE; METAL-COMPLEXES; STRUCTURAL-CHARACTERIZATION; POLY(PROPYLENE CARBONATE); CO2/EPOXIDE COPOLYMERIZATION; MECHANISTIC INSIGHTS; TRIBLOCK COPOLYMERS;

D O I：

10.1002/anie.201709218

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A new family of heterometallic catalysts based on trimetalated macrocyclic tris(salen) ligands and rare-earth metals was prepared and structurally characterized. The LaZn3 system containing anionic ligands such as acetate plays a critical role in catalyzing the alternating copolymerization of cyclohexene oxide (CHO) and CO2 with a high proportion of carbonate linkages. Among the lanthanide metals, the CeZn3 system exhibits high catalytic activity with a turnover frequency (TOF) of over 370 h(-1). NMR analysis of the complex and end-group analysis of the polymer suggest that the acetate ligands are rapidly exchanged, not only among coordinated acetates, but also between coordinated acetates and added carboxylate anions. These unique properties make this the first example of telomerization for the copolymerization of CHO and CO2.

引用

页码：2492 / 2496

页数：5

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