Initiating abilities of diphosphine- and diamine-ligated Pd complexes/NaBPh<sub>4</sub> systems for C1 polymerization of diazoacetates
Initiating abilities of diphosphine- and diamine-ligated Pd complexes/NaBPh<sub>4</sub> systems for C1 polymerization of diazoacetates
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二膦和二胺连接的 Pd 配合物/NaBPh<sub>4</sub> 体系对重氮乙酸酯 C1 聚合的引发能力
DOI：
10.1039/d2py01548j
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发表时间：
2023
影响因子：
4.6
通讯作者：
Ihara Eiji
中科院分区：
文献类型：
--
作者：
Shimomoto Hiroaki;Miyano Yuto;Kinoshita Kaito;Itoh Tomomichi;Ihara Eiji
新制备了一系列以二膦或二胺和二氯醌衍生物为配体的钯配合物，并研究了它们与NaBPh4共同引发重氮乙酸酯C1聚合的能力。在本文研究的（二膦）Pd(II)Cl（Cl-醌基）配合物中，方形平面顺式（二膦：二苯基膦-二铁二烯）和扭曲的方形平面反式（二膦：黄磷）与NaBPh4的配合物从重氮乙酸乙酯中得到了高度平行的聚合物，尽管聚合物收率很低。一系列含有双齿二胺的Pd(0)配合物，如N，N,N ',N ' -四甲基-1,3-丙二胺和2,3-二氯萘醌，与NaBPh4结合可聚合重氮乙酸酯，以中等产率获得中等双聚性聚合物，表明（二胺）Pd(0)（二氯醌）框架可能是一个有希望的通用平台，用于重氮乙酸酯的C1聚合具有高活性和立体选择性的引发体系。
A series of well-defined Pd complexes bearing diphosphines or diamines and a dichloroquinone-derived unit as ligands were newly prepared and their initiating abilities in conjunction with NaBPh4 for the C1 polymerization of diazoacetates were investigated. Among the (diphosphine)Pd(II)Cl(Cl-quinonyl) complexes examined here, square planar cis (diphosphine: diphenylphosphinoferrocene) and distorted square planar trans (diphosphine: xantphos) complexes with NaBPh4 yielded highly syndiotactic polymers from ethyl diazoacetate despite low polymer yields. A series of Pd(0) complexes bearing a bidentate diamine such as N,N,N′,N′-tetramethyl-1,3-propanediamine and 2,3-dichloronaphthoquinone in conjunction with NaBPh4 polymerized diazoacetates to afford moderately syndiotactic polymers in moderate yields, indicating that the (diamine)Pd(0)(dichloroquinone) framework could be a promising general platform for an initiating system with high activity and stereoselectivity for the C1 polymerization of diazoacetates.