The intramolecularly bridged alkyl cobaltic complexes are one of important coenzyme B12 model coplexes. In this paper, study on the thermolytic reaction of aqua(3 bromopropyl)cobaloximes in solution revealed that a ne...The intramolecularly bridged alkyl cobaltic complexes are one of important coenzyme B12 model coplexes. In this paper, study on the thermolytic reaction of aqua(3 bromopropyl)cobaloximes in solution revealed that a new intramolecularly bridged alkyl cobaloximes complex was formed and the reaction is influenced by tempertature and solvent. Adding cyclodxtrin has no obvious effect to the rate of the reaction, but various products with different axial bases were obtained. The intramolecularly bridged alkyl cobaloxime complex (bromo(O trimethylene dimethy lglyoxime)(dimethylglyoximate)cobalt?) was characterized by EA and ESI MS. Thermogravimetric analysis of this complex found that a carbon radical that from homolysis of the Co C bond is retained in the proximity of CoⅡ complex, which is very similar to the behavior of coenzyme B12.展开更多
合成了一种N,N-二齿配位的新型树枝状桥联吡啶亚胺配体及其镍配合物,利用元素分析、傅里叶变换红外光谱（FTIR）和电喷雾电离质谱（ESI-MS）对其结构进行了表征.以二氯乙基铝（Et Al Cl2）为助催化剂,考察了树枝状桥联镍配合物催化乙烯...合成了一种N,N-二齿配位的新型树枝状桥联吡啶亚胺配体及其镍配合物,利用元素分析、傅里叶变换红外光谱（FTIR）和电喷雾电离质谱（ESI-MS）对其结构进行了表征.以二氯乙基铝（Et Al Cl2）为助催化剂,考察了树枝状桥联镍配合物催化乙烯齐聚和1-戊烯齐聚的聚合条件对产物分布的影响.结果表明,当聚合时间为60 min,聚合压力为0.5 MPa,Al/Ni摩尔比为150时,乙烯齐聚产物中C10~C14的选择性最高,达到93%,催化活性为0.99×106g/（mol Ni·h）;当聚合时间为60 min,Al/Ni摩尔比为300时,1-戊烯齐聚产物中C20的选择性最高为70.5%,催化活性为2.47×105g/（mol Ni·h）.该树枝状桥联镍配合物对乙烯齐聚反应和1-戊烯齐聚反应均具有良好的催化活性和较高碳数的齐聚产物选择性.展开更多
文摘The intramolecularly bridged alkyl cobaltic complexes are one of important coenzyme B12 model coplexes. In this paper, study on the thermolytic reaction of aqua(3 bromopropyl)cobaloximes in solution revealed that a new intramolecularly bridged alkyl cobaloximes complex was formed and the reaction is influenced by tempertature and solvent. Adding cyclodxtrin has no obvious effect to the rate of the reaction, but various products with different axial bases were obtained. The intramolecularly bridged alkyl cobaloxime complex (bromo(O trimethylene dimethy lglyoxime)(dimethylglyoximate)cobalt?) was characterized by EA and ESI MS. Thermogravimetric analysis of this complex found that a carbon radical that from homolysis of the Co C bond is retained in the proximity of CoⅡ complex, which is very similar to the behavior of coenzyme B12.
