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Synthesis and characterization of α-diamine palladium complexes and insight into hybridization effects of nitrogen donor atoms on norbornene (co)polymerizations†
Polymer Chemistry ( IF 4.6 ) Pub Date : 2018-05-04 00:00:00 , DOI: 10.1039/c8py00395e Ting Zheng 1, 2, 3, 4, 5 , Heng Liao 1, 2, 3, 4, 5 , Jie Gao 1, 2, 3, 4, 5 , Liu Zhong 1, 2, 3, 4, 5 , Haiyang Gao 1, 2, 3, 4, 5 , Qing Wu 1, 2, 3, 4, 5
Polymer Chemistry ( IF 4.6 ) Pub Date : 2018-05-04 00:00:00 , DOI: 10.1039/c8py00395e Ting Zheng 1, 2, 3, 4, 5 , Heng Liao 1, 2, 3, 4, 5 , Jie Gao 1, 2, 3, 4, 5 , Liu Zhong 1, 2, 3, 4, 5 , Haiyang Gao 1, 2, 3, 4, 5 , Qing Wu 1, 2, 3, 4, 5
Affiliation
Ligand donor atoms play an important role in catalytic olefin polymerization. The nitrogen atom is easily ligated to the metal center with different hybridizations, which is widely applied in the synthesis of palladium complexes. We have herein reported the synthesis and characterization of a series of α-diamine palladium complexes featuring two sp3 hybridized nitrogen donor atoms and their catalytic properties toward norbornene (NBE) (co)polymerizations. α-Diamine palladium catalysts showed a very high activity up to 7.02 × 107 g PNBE per mol Pd per h for norbornene polymerization. The hybridization effects of nitrogen donor atoms on homo- and copolymerizations of norbornene and polar norbornene monomers with palladium complexes bearing α-diamine, amine-imine, and α-diimine ligands activated by methylaluminoxane (MAO) were studied systematically. With variation of the two nitrogen donor atoms from the amine nitrogen with sp3 hybridization to the imine nitrogen with sp2 hybridization, homo- and copolymerization activities of the palladium catalysts decreased consistently. The molecular structure analysis of the palladium complexes showed that the ligand redistribution reaction and more electrophilic palladium center led to high activity for norbornene polymerization using α-diamine palladium catalysts.
中文翻译:
α-二胺钯配合物的合成和表征,以及氮供体原子对降冰片烯(共)聚合的杂化作用的见解†
配体供体原子在催化烯烃聚合中起重要作用。氮原子易于通过不同的杂交连接到金属中心,广泛用于钯配合物的合成中。我们已经在本文中报道了一系列具有两个sp 3杂化的氮供体原子的α-二胺钯配合物的合成和表征,以及它们对降冰片烯(NBE)(共)聚合的催化性能。α-二胺钯催化剂显示出高达7.02×10 7的极高活性对于降冰片烯聚合反应,每mol Pd / h含PNBE g。系统研究了氮供体原子对降冰片烯和极性降冰片烯单体与甲基铝氧烷(MAO)活化的带有α-二胺,胺-亚胺和α-二亚胺配体的钯配合物的均聚和共聚的影响。随着两个氮供体原子从通过sp 3杂交的胺氮到通过sp 2杂交的亚胺氮变化,钯催化剂的均相和共聚活性不断降低。钯配合物的分子结构分析表明,配体再分布反应和更多的亲电钯中心导致使用α-二胺钯催化剂的降冰片烯聚合反应具有高活性。
更新日期:2018-05-04
中文翻译:
α-二胺钯配合物的合成和表征,以及氮供体原子对降冰片烯(共)聚合的杂化作用的见解†
配体供体原子在催化烯烃聚合中起重要作用。氮原子易于通过不同的杂交连接到金属中心,广泛用于钯配合物的合成中。我们已经在本文中报道了一系列具有两个sp 3杂化的氮供体原子的α-二胺钯配合物的合成和表征,以及它们对降冰片烯(NBE)(共)聚合的催化性能。α-二胺钯催化剂显示出高达7.02×10 7的极高活性对于降冰片烯聚合反应,每mol Pd / h含PNBE g。系统研究了氮供体原子对降冰片烯和极性降冰片烯单体与甲基铝氧烷(MAO)活化的带有α-二胺,胺-亚胺和α-二亚胺配体的钯配合物的均聚和共聚的影响。随着两个氮供体原子从通过sp 3杂交的胺氮到通过sp 2杂交的亚胺氮变化,钯催化剂的均相和共聚活性不断降低。钯配合物的分子结构分析表明,配体再分布反应和更多的亲电钯中心导致使用α-二胺钯催化剂的降冰片烯聚合反应具有高活性。