Highly efficient solvent-free coupling reaction of carbon dioxide(CO2)and epichlorohydrin catalyzed by meso-tetraphenyl porphyrin magnesium(MgTPP)in the presence of triethylamine as co-catalysts is reported.As a chlor...Highly efficient solvent-free coupling reaction of carbon dioxide(CO2)and epichlorohydrin catalyzed by meso-tetraphenyl porphyrin magnesium(MgTPP)in the presence of triethylamine as co-catalysts is reported.As a chlorophyll-like catalyst,MgTPP showed excellent activity for the coupling reaction of CO2 and epichlorohydrin to chloropropene carbonate,in which the turnover number could reach up to 9200.Moreover,different factors including the amount of catalyst,reaction temperature,pressure and time were systematically investigated and the optimal reaction conditions were obtained(epichlorohydrin 50 mmol,MgTPP 5.0×10- 3mmol,triethylamine 6.25×10-3 mmol,140°C,1.5 MPa,8 h).A plausible two-pathway mechanism for the coupling reaction of CO 2and epichlorohydrin is proposed to propound the catalysis of MgTPP.展开更多
The development of routes and strategies for the design and preparation of complexes of 4d metals in moderate oxidation states is of great importance in magnetochemistry, bioinorganic chemistry, materials chemistry an...The development of routes and strategies for the design and preparation of complexes of 4d metals in moderate oxidation states is of great importance in magnetochemistry, bioinorganic chemistry, materials chemistry and solid-state chemistry. Bidentate ligands containing N or O donors especially phenanthroline have been widely used to form complexes with interesting structural motif. Reaction of M(CO)6 (M = Cr, Mo, W) with phenanthroline has been done in 1935 and produced an interesting stereo structure, but the reaction of MoOE(acac)2 (acac = acetylacetonato) with phenanthroline has not been studied yet. So, in this research, first of all MoOE(acac) 2 was prepared, and then it reacted with bidentate nitrogen donor to lead to produce the complex of [MoOEL2] (L = Phen) and different aspects of this complex were studied. This complex is very active and highly selective epoxidation catalyst. The structure of the product was characterized by various spectral techniques such as elemental analysis, IH NMR, 13C NMR and IR spectroscopy.展开更多
基金Supported by the National Natural Science Foundation of China(21036009,20776003,20976203)the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality(PHR201107104,PHR200907105)the Higher-level Talent Project for Guangdong Provincial Universities and the Fundamental Research Funds for the Central Universities
文摘Highly efficient solvent-free coupling reaction of carbon dioxide(CO2)and epichlorohydrin catalyzed by meso-tetraphenyl porphyrin magnesium(MgTPP)in the presence of triethylamine as co-catalysts is reported.As a chlorophyll-like catalyst,MgTPP showed excellent activity for the coupling reaction of CO2 and epichlorohydrin to chloropropene carbonate,in which the turnover number could reach up to 9200.Moreover,different factors including the amount of catalyst,reaction temperature,pressure and time were systematically investigated and the optimal reaction conditions were obtained(epichlorohydrin 50 mmol,MgTPP 5.0×10- 3mmol,triethylamine 6.25×10-3 mmol,140°C,1.5 MPa,8 h).A plausible two-pathway mechanism for the coupling reaction of CO 2and epichlorohydrin is proposed to propound the catalysis of MgTPP.
文摘The development of routes and strategies for the design and preparation of complexes of 4d metals in moderate oxidation states is of great importance in magnetochemistry, bioinorganic chemistry, materials chemistry and solid-state chemistry. Bidentate ligands containing N or O donors especially phenanthroline have been widely used to form complexes with interesting structural motif. Reaction of M(CO)6 (M = Cr, Mo, W) with phenanthroline has been done in 1935 and produced an interesting stereo structure, but the reaction of MoOE(acac)2 (acac = acetylacetonato) with phenanthroline has not been studied yet. So, in this research, first of all MoOE(acac) 2 was prepared, and then it reacted with bidentate nitrogen donor to lead to produce the complex of [MoOEL2] (L = Phen) and different aspects of this complex were studied. This complex is very active and highly selective epoxidation catalyst. The structure of the product was characterized by various spectral techniques such as elemental analysis, IH NMR, 13C NMR and IR spectroscopy.