A series of N-base appended corroles and their manganese complexes were synthesized and their binding constants with three different nitrogenous ligands, triethylamine, N-methylimidazole and pyridine, were evaluated b...A series of N-base appended corroles and their manganese complexes were synthesized and their binding constants with three different nitrogenous ligands, triethylamine, N-methylimidazole and pyridine, were evaluated by spectroscopy. Kinetic studies indicated that the presence of appended N- donor ligands may cause a significant enhancement of the rate of oxygen atom transfers （OAT） from （oxo）manganese（V） corrole to alkene, and the stronger axial ligand binding has impact on the rate of the oxidation reaction. Turnover frequency （TOF） for the catalytic oxidation of alkenes by appended manganese corroles varies with the following ligand order： acetamido 〈 pyridyl 〈 imidazolyl. The influence of the external axial ligands on the catalytic epoxidation was investigated by using appended acetamido manganese corrole as catalyst, with the results revealing that N-methylimidazole gave the best enhancement on the yields of total oxidation products among the investigated nitrogenous ligands.展开更多
The effects of peptides, amino acids and organic bases as axial ligands on reaction activities in the electrocarboxylation of benzyl chloride with CO2 catalyzed by CoTPP are reported. Imidazole, peptide containing -SH...The effects of peptides, amino acids and organic bases as axial ligands on reaction activities in the electrocarboxylation of benzyl chloride with CO2 catalyzed by CoTPP are reported. Imidazole, peptide containing -SH and amino acid containing imi dazyl can enhance the catalytic activity. As an axial ligand, imidazole is the best one, it can make the current efficency of electrocarboxylation catalyzed by CoTPP rising about 23%. The effects of different amount of imidazole on CoTPP’s catalytic activities have been studied, and the cause of these effects have been explaind predrinarily.展开更多
基金supported by National Natural Science Foundation of China(Nos.21171057,21371059)Research Grant Councilof Hong Kong under project HKUST6182/99pArea of Excellence Scheme(No.AoE/P-10/01)
文摘A series of N-base appended corroles and their manganese complexes were synthesized and their binding constants with three different nitrogenous ligands, triethylamine, N-methylimidazole and pyridine, were evaluated by spectroscopy. Kinetic studies indicated that the presence of appended N- donor ligands may cause a significant enhancement of the rate of oxygen atom transfers （OAT） from （oxo）manganese（V） corrole to alkene, and the stronger axial ligand binding has impact on the rate of the oxidation reaction. Turnover frequency （TOF） for the catalytic oxidation of alkenes by appended manganese corroles varies with the following ligand order： acetamido 〈 pyridyl 〈 imidazolyl. The influence of the external axial ligands on the catalytic epoxidation was investigated by using appended acetamido manganese corrole as catalyst, with the results revealing that N-methylimidazole gave the best enhancement on the yields of total oxidation products among the investigated nitrogenous ligands.
文摘The effects of peptides, amino acids and organic bases as axial ligands on reaction activities in the electrocarboxylation of benzyl chloride with CO2 catalyzed by CoTPP are reported. Imidazole, peptide containing -SH and amino acid containing imi dazyl can enhance the catalytic activity. As an axial ligand, imidazole is the best one, it can make the current efficency of electrocarboxylation catalyzed by CoTPP rising about 23%. The effects of different amount of imidazole on CoTPP’s catalytic activities have been studied, and the cause of these effects have been explaind predrinarily.
