Highly Active Di- and Trimetallic Cobalt Catalysts for the Copolymerization of CHO and CO2 at Atmospheric Pressure
Highly Active Di- and Trimetallic Cobalt Catalysts for the Copolymerization of CHO and CO2 at Atmospheric Pressure
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DOI：
10.1021/ma902582m
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发表时间：
2010-03-09
期刊：
影响因子：
5.5
通讯作者：
Williams, Charlotte K.
中科院分区：
文献类型：
--
作者：
Kember, Michael R.;White, Andrew J. P.;Williams, Charlotte K.
报道了三种新型二氧化碳与环氧环己烷共聚钴催化剂的合成与表征。所有的配合物在只有1个大气压的二氧化碳压力下都非常活跃，对共聚和碳酸盐形成具有非常高的选择性。催化剂是由大环的、还原的“Robson”型辅助配体和乙酸酯基团配位的二钴（II/II和II/III）和三钴（II/II/II）络合物。配合物是显着更积极的比他们的直接锌类似物，我们归因于增加的亲核性的钴-氧键中的钴碳酸盐繁殖物种。所有这三种配合物的特征在于使用质谱，红外和紫外-可见光谱，元素分析，以及，对于三钴配合物和混合价二钴物种，单晶X-射线晶体学。
The synthesis and characterization of three new cobalt catalysts for the copolymerization of carbon dioxide and cyclohexene oxide are reported. All the complexes are extremely active at just 1 atm pressure of carbon dioxide, with very high selectivity for copolymerization and carbonate formation. The catalysts are dicobalt(II/II and II/III) and tricobalt(II/II/II) complexes coordinated by a macrocyclic, reduced "Robson" type ancillary ligand and by acetate groups. The complexes are significantly more active than their direct zinc analogues, which we attribute to the increased nucleophilicity of the cobalt-oxygen bond in the cobalt-carbonate propagating species. All three complexes are characterized using mass spectrometry, infrared and ultraviolet-visible spectroscopies, elemental analysis, and, for the tricobalt complex and mixed valence dicobalt species, single-crystal X-ray crystallography.