Polymerization of Alkyl Diazoacetates Initiated by Pd(Naphthoquinone)/Borate Systems: Dual Role of Naphthoquinones as Oxidant and Anionic Ligand for Generating Active Pd(II) Species
Polymerization of Alkyl Diazoacetates Initiated by Pd(Naphthoquinone)/Borate Systems: Dual Role of Naphthoquinones as Oxidant and Anionic Ligand for Generating Active Pd(II) Species
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DOI：
10.1021/acs.macromol.9b00857
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发表时间：
2019-09
期刊：
影响因子：
5.5
通讯作者：
Hiroaki Shimomoto;Shohei Ichihara;Hinano Hayashi;T. Itoh;E. Ihara
中科院分区：
文献类型：
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作者：
Hiroaki Shimomoto;Shohei Ichihara;Hinano Hayashi;T. Itoh;E. Ihara
以1，4-萘醌（NQ）或其衍生物为配体的钯配合物与硼酸盐NaBPh_4组成的复合体系是一种有效的引发体系。重氮乙酸乙酯与含两个NQ分子的Pd（0）配合物[Pd（nq）_2]和NaBPh_4进行聚合反应，得到分子量较高（Mn = 36 kDa）的聚乙氧羰基亚甲基，产率约为70%。该引发体系对其它重氮乙酸酯、苄基和环己基重氮乙酸酯的聚合也有效。此外，在NaBPh 4存在下，合成了一种新型的带有2，3-二氯-1，4-萘醌衍生的阴离子萘醌配体的Pd（II）配合物（甲磺隆），[Pd（cod）（Cl-nq）Cl]（cod = 1，5-环辛烯），它是由Pd（0）前体Pd 2（dba）3·CHCl 3 [dba =（E，E）-二亚苄基丙酮]与COD和三羟甲基丙酮反应新制得的，与以前的聚合物相比，能够提供具有更高立构规整性的聚（烷氧基羰基亚甲基）。
For polymerization of alkyl diazoacetates, the combination of a Pd complex bearing 1,4-naphthoquinone (NQ) or its derivatives as a ligand and borate, NaBPh4, was found to be an efficient initiating system. The polymerization of ethyl diazoacetate by a Pd(0) complex having two NQ molecules [Pd(nq)2] with NaBPh4 proceeded to give poly(ethoxycarbonylmethylene)s with a relatively high molecular weight (up to Mn = 36 kDa) in good yield (∼70%). This initiating system was also effective for polymerizing other diazoacetates, benzyl and cyclohexyl diazoacetates. In addition, in the presence of NaBPh4, a novel Pd(II) complex bearing an anionic naphthoquinonyl ligand derived from 2,3-dichloro-1,4-naphthoquinone (dichlone), [Pd(cod)(Cl-nq)Cl] (cod = 1,5-cyclooctadiene), which was newly prepared by treatment of a Pd(0) precursor, Pd2(dba)3·CHCl3 [dba = (E,E)-dibenzylideneacetone], with COD and dichlone, was capable of affording poly(alkoxycarbonylmethylene)s with much higher stereoregularity compared to the previously...