Redox Control of a Ring-Opening Polymerization Catalyst
Redox Control of a Ring-Opening Polymerization Catalyst
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DOI：
10.1021/ja2036089
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发表时间：
2011-06-22
影响因子：
15
通讯作者：
Diaconescu, Paula L.
中科院分区：
文献类型：
--
作者：
Broderick, Erin M.;Guo, Neng;Diaconescu, Paula L.
在L-丙交酯的开环聚合过程中，使用氧化还原试剂控制二茂铁基配体负载的钇醇盐络合物的活性。通过X射线晶体学和H-1 NMR、XANES和穆斯堡尔谱对氧化络合物进行了表征。氧化和还原的钇络合物之间的原位切换导致L-丙交酯的聚合速率的变化。通过凝胶渗透色谱法分析合成的聚合物。三亚甲基碳酸酯的聚合也进行了还原和氧化形式的铟醇盐络合物。铟系统表现出与钇相反的行为，揭示了基于金属的聚合速率依赖性。
The activity of an yttrium alkoxide complex supported by a ferrocene-based ligand was controlled using redox reagents during the ring-opening polymerization of L-lactide. The oxidized complex was characterized by X-ray crystallography and H-1 NMR, XANES, and Mossbauer spectroscopy. Switching in situ between the oxidized and reduced yttrium complexes resulted in a change in the rate of polymerization of L-lactide. Synthesized polymers were analyzed by gel permeation chromatography. Polymerization of trimethylene carbonate was also performed with the reduced and oxidized forms of an indium alkoxide complex. The indium system showed the opposite behavior to that of yttrium, revealing a metal-based dependency on the rate of polymerization.