Bimetallic Coordination Insertion Polymerization of Unprotected Polar Monomers: Copolymerization of Amino Olefins and Ethylene by Dinickel Bisphenoxyiminato Catalysts
作者:Madalyn R. Radlauer、Aya K. Buckley、Lawrence M. Henling、Theodor Agapie
DOI:10.1021/ja4004816
日期:2013.3.13
bisphenoxyiminato complexes based on highlysubstituted p- and m-terphenyl backbones were synthesized, and the corresponding atropisomers were isolated. In the presence of a phosphine scavenger, Ni(COD)2, the phosphine-ligated syn-dinickel complexes copolymerized α-olefins and ethylene in the presence of amines to afford 0.2-1.3% α-olefin incorporation and copolymerized amino olefins and ethylene with a similar
Olefin Polymerization by Dinuclear Zirconium Catalysts Based on Rigid Teraryl Frameworks: Effects on Tacticity and Copolymerization Behavior
作者:Jessica Sampson、Gyeongshin Choi、Muhammed Naseem Akhtar、E. A. Jaseer、Rajesh Theravalappil、Hassan Ali Al-Muallem、Theodor Agapie
DOI:10.1021/acs.organomet.7b00015
日期:2017.5.22
of bimetallic catalysts for olefin polymerization, a series of structurally related binuclear zirconium catalysts with bisamine bisphenolate and pyridine bisphenolate ligands connected by rigid teraryl units were synthesized. Anthracene-9,10-diyl and 2,3,5,6-tetramethylbenzene-1,4-diyl were employed as linkers. Bulky SiiPr3 and SiPh3 substituents were used in the position ortho to the phenolate oxygen
为了深入了解用于烯烃聚合的双金属催化剂的行为,合成了一系列结构相关的双核锆催化剂,其中双胺双酚盐和吡啶双酚盐配体通过刚性三芳基单元连接。蒽-9,10-二基和2,3,5,6-四甲基苯-1,4-二基用作连接基。在酚盐氧的邻位使用大的Si i Pr 3和SiPh 3取代基。伪Ç小号和Ç 2观察到双胺双酚盐配体的双核配合物存在对称异构体。通常,与单锆类似物相比,双核催化剂显示出更高的全同立构规整度,异构体之间存在一些差异。发现存在双胺胺的双酚盐二锆络合物具有中等活性(最高达1.5 kg mmol Zr –1 h –1),可在存在下将1-己烯聚合为等规富集的聚1-己烯(高达45%mmmm)。化学计量的三苯甲基或苯甲酸硼酸盐活化剂。在生产等规富集聚丙烯的过程中观察到中等活性(最高2.8 kg mmol Zr –1 h –1和最高25.4%mmmm)。先前提出的基于来自第二金属位点的远端空间效应的立构规
Dinickel Bisphenoxyiminato Complexes for the Polymerization of Ethylene and α-Olefins
作者:Madalyn R. Radlauer、Michael W. Day、Theodor Agapie
DOI:10.1021/om2011694
日期:2012.3.26
The corresponding syn and anti dinickel complexes (25-s and 25-a) were synthesized and characterized by single-crystal X-ray diffraction. These frameworks limit the relative movement of the metal centers, restricting the metal–metal distance. Kinetics studies of isomerization of a ligand precursor (7-a) allowed the calculation of the activation parameters for the isomerization process (ΔH⧧ = 28.0
报道了基于刚性对三联苯骨架的双核苯氧基亚氨基镍烯烃聚合催化剂。三联苯单元的中心芳烃的全甲基化和芳基-芳基键邻位的外围环的氧取代阻止了这些键周围的旋转,从而使配体的阻转异构体得以分离。合成了相应的顺和反二镍配合物(25-s和25-a),并通过单晶 X 射线衍射表征。这些框架限制了金属中心的相对运动,限制了金属-金属的距离。配体前体 ( 7-a )异构化的动力学研究允许计算异构化过程的活化参数 (ΔH⧧ = 28.0 ± 0.4 kcal × mol –1和 Δ S⧧ = −12.3 ± 0.4 cal mol –1 K –1 )。报道的镍配合物对乙烯聚合(TOF 高达 3700(mol C 2 H 4)(mol Ni)-1 h –1)和乙烯/α-烯烃共聚具有活性。在乙烯的聚合中只观察到甲基支链,而α-烯烃的加入没有明显的链行走。这些催化剂在极性添加剂存在下和在纯四氢呋喃中是有活性的。顺式和反