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Aluminum and Titanium Complexes Containing Pyrrole-imine Ligands: Syntheses, Structures, and Ring-opening Polymerization of ε-Caprolactone

Aluminum and Titanium Complexes Containing Pyrrole-imine Ligands: Syntheses, Structures, and Ring-opening Polymerization of ε-Caprolactone
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摘要 Syntheses and properties of aluminum and titanium complexes incorporating the pyrrole-imine ligands,N-((1H-pyrrol-2-yl)methyl)-1-(1H-pyrrol-2-yl)methanimine(H2L^1)and 2-cyano-1H-pyrrole(HL^2),have been investigated.Addition of one equiv of H2L^1 to AlMe3 and AlEt3,respectively results in the formation of dinuclear complexes[Al2(L^1)2 Me2](1)and[Al2(L^1)2 Et2](2).Treatment of Ti(NMe2)4 with one equiv of HL^2 and two equiv of iPrOH or three equiv of BnOH results in the production of complexes[Ti(HL^3)2(OiPr)2](3)and[Ti2(HL^3)2(OBn)6](4)(H2L^3=N,N-dimethyl-1H-pyrrole-2-carboximid-amide).HL^3 anion is an intermediate which is in situ formed from the reaction of HL^2 and Ti(NMe2)4.The structures of 1~4 were characterized by single crystal X-ray diffraction.The catalytic properties of 1~4 toward ring-opening polymerization(ROP)ofε-caprolactone were studied.All of the compounds could effectively initiate the polymerization reactions with good activities. Syntheses and properties of aluminum and titanium complexes incorporating the pyrrole-imine ligands, N-((1H-pyrrol-2-yl)methyl)-1-(1H-pyrrol-2-yl)methanimine(H2L1) and 2-cyano-1H-pyrrole(HL2), have been investigated. Addition of one equiv of H2L1 to AlMe3 and AlEt3, respectively results in the formation of dinuclear complexes [Al2(L1)2 Me2](1) and [Al2(L1)2 Et2](2). Treatment of Ti(NMe2)4 with one equiv of HL2 and two equiv of iPrOH or three equiv of BnOH results in the production of complexes [Ti(HL3)2(OiPr)2](3) and [Ti2(HL3)2(OBn)6](4)(H2L3 = N,N-dimethyl-1H-pyrrole-2-carboximid-amide). HL3 anion is an intermediate which is in situ formed from the reaction of HL2 and Ti(NMe2)4. The structures of 1~4 were characterized by single crystal X-ray diffraction. The catalytic properties of 1~4 toward ring-opening polymerization(ROP) of ε-caprolactone were studied. All of the compounds could effectively initiate the polymerization reactions with good activities.
机构地区 College of Chemistry
出处 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2019年第10期1797-1806,1613,共11页 结构化学(英文)
基金 supported by the National Natural Science Foundation of China(21772140) Natural Science Foundation of Jiangsu Province(BK20171213) the Priority Academic Program Development of Jiangsu Higher Education Institution
关键词 ALUMINUM titanium pyrrole-imine Ε-CAPROLACTONE RING-OPENING polymerization aluminum titanium pyrrole-imine ε-caprolactone ring-opening polymerization
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