Synthesis of Mono- and Dinuclear Aluminum Complexes Bearing Aromatic Amino-Phenolato Ligands: A Comparative Study in the Ring-Opening Polymerization of Cyclohexene Oxide

被引：6

作者：

Chen, Yongjie ^{[1
]}

Li, Baoxia ^{[1
]}

Wang, Yaorong ^{[1
]}

Zhu, Xuehua ^{[2
]}

Yuan, Dan ^{[1
]}

Yao, Yingming ^{[1
]}

机构：

[1] Soochow Univ, Coll Chem Chem Engn & Mat Sci, Key Lab Organ Synth Jiangsu Prov, Suzhou 215123, Peoples R China

[2] Suzhou Univ Sci & Technol, Sch Chem & Life Sci, Suzhou 215009, Peoples R China

来源：

INORGANIC CHEMISTRY | 2023年 / 62卷 / 51期

基金：

中国国家自然科学基金;

关键词：

EPOXIDE POLYMERIZATION; EPSILON-CAPROLACTONE; ALTERNATING COPOLYMERIZATION; STRUCTURAL-CHARACTERIZATION; LACTIDE POLYMERIZATION; ACTIVE CATALYSTS; ZINC; POLYETHERS; MECHANISM; ALKYL;

D O I：

10.1021/acs.inorgchem.3c03318

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Dinuclear aluminum methyl complexes bearing aromatic diamine-bridged tetra(phenolato) ligands and the mononuclear aluminum methyl complex with the phenylamine-bridged bis(phenolato) ligand have been synthesized and characterized. Structure determination revealed that the Al-Al distances in these dinuclear aluminum complexes are tunable by the choice of the suitable aromatic backbone of the diamine-bridged tetra(phenolato) ligands. The catalytic behaviors of these mono- and dinuclear aluminum complexes for cyclohexene oxide (CHO) polymerization were investigated. The activities of these dinuclear Al complexes were observed to increase with the decrease of Al-Al distances, and the dinuclear Al complexes appeared to have better catalytic activity than the mononuclear Al complex, even if the Al-Al distance is as long as 9.401 & Aring;. Dinuclear aluminum complex 2, with the shortest Al-Al distance (7.236 & Aring;), showed the highest activity toward CHO polymerization with TOFs up to 6460 h(-1) in neat CHO at 30 degrees C. Furthermore, comparative kinetic studies revealed that the polymerization is first-order for CHO concentration, and the reaction orders for initiator concentration are different for the mono- and dinuclear Al complexes. The polymerization mechanism study revealed that both the methyl and phenolate groups were involved in the initiation process.

引用

页码：21247 / 21256

页数：10

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