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Synthesis and Characterization of Cobalt(II/II) and Cobalt(II/III) Macrocyclic Complexes and Their Application in the Copolymerization of Epoxides and CO2
Organometallics ( IF 2.5 ) Pub Date : 2023-05-26 , DOI: 10.1021/acs.organomet.3c00154 Yanwei Wang 1 , Xuehua Zhu 2 , Yong Zhang 3 , Dan Yuan 1 , Yingming Yao 1
Organometallics ( IF 2.5 ) Pub Date : 2023-05-26 , DOI: 10.1021/acs.organomet.3c00154 Yanwei Wang 1 , Xuehua Zhu 2 , Yong Zhang 3 , Dan Yuan 1 , Yingming Yao 1
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The synthesis and characterization of six dinuclear cobalt complexes bearing a conjugated macrocyclic ligand are reported. The condensation of 2,6-diformylphenol and o-phenylenediamine led to semi-hydrogenated macrocycles A–C. The ligand precursor A reacted with Co(OAc)2·4H2O and generated the Co(II/II) complex 1, and a conjugated macrocyclic ligand was formed during the complexation. The partial oxidation of 1 with air resulted in mixed-valence Co(II/III) complexes 2 and 3 bearing different anionic ligands. Analogous Co(II/III) complexes 4–6 of Cl- and F-substituted ligand backbones were also synthesized. Structural characterization and charge determination of all complexes were achieved through X-ray diffraction analysis and X-ray photoelectron spectroscopy. These complexes were applied in the copolymerization of CO2 and cyclohexene oxide (CHO), and the mixed valence Co(II/III) complex 2 showed good reactivity and selectivity (>99% polycarbonate).
中文翻译：
钴(II/II)和钴(II/III)大环配合物的合成、表征及其在环氧化物和CO2共聚中的应用
报道了六种带有共轭大环配体的双核钴配合物的合成和表征。2,6-二甲酰基苯酚和邻苯二胺的缩合产生半氢化大环A-C。配体前体A与Co(OAc) 2 ·4H 2 O反应生成Co(II/II)配合物1，络合过程中形成共轭大环配体。1用空气部分氧化生成带有不同阴离子配体的混合价 Co(II/III) 配合物2和3 。类似的 Co(II/III) 配合物4–6还合成了Cl-和F-取代的配体主链。所有配合物的结构表征和电荷测定均通过 X 射线衍射分析和 X 射线光电子能谱进行。这些配合物应用于CO 2和环己烯氧化物(CHO)的共聚中，混合价Co(II/III)配合物2表现出良好的反应活性和选择性(>99%聚碳酸酯)。
更新日期：2023-05-26
中文翻译：
钴(II/II)和钴(II/III)大环配合物的合成、表征及其在环氧化物和CO2共聚中的应用
报道了六种带有共轭大环配体的双核钴配合物的合成和表征。2,6-二甲酰基苯酚和邻苯二胺的缩合产生半氢化大环A-C。配体前体A与Co(OAc) 2 ·4H 2 O反应生成Co(II/II)配合物1，络合过程中形成共轭大环配体。1用空气部分氧化生成带有不同阴离子配体的混合价 Co(II/III) 配合物2和3 。类似的 Co(II/III) 配合物4–6还合成了Cl-和F-取代的配体主链。所有配合物的结构表征和电荷测定均通过 X 射线衍射分析和 X 射线光电子能谱进行。这些配合物应用于CO 2和环己烯氧化物(CHO)的共聚中，混合价Co(II/III)配合物2表现出良好的反应活性和选择性(>99%聚碳酸酯)。
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