Located in the middle of the fever to solve the problem of CO_(2)emissions in the environment,CO_(2)sequestration by reaction with epoxides is one of the key tools,as it not only fixes CO_(2),but also makes it functio...Located in the middle of the fever to solve the problem of CO_(2)emissions in the environment,CO_(2)sequestration by reaction with epoxides is one of the key tools,as it not only fixes CO_(2),but also makes it functional by leading to cyclic carbonates.Herein,the results are focused specifically on the formation of cyclic organic carbonates catalyzed by metal-salen complexes,previously achieved with yttrium and scandium,that are compared with those of analogous complexes containing metals from the first transition series,such as cobalt or chromium.Density functional theory(DFT)calculations allow to determine whether this switch of metals will be feasible and provide the basis for instigating future experimental efforts in this regard.The calculations analyzing the structure and electronics of the catalysts allow us to give not only a clear picture of whether these catalysts will be efficient,but also allow us to assess which metal center is the most convenient and/or whether the catalytic reaction will occur under mild conditions.Advanced buried volume calculations with the SambVca packages shed light on the different catalytic pockets of monometallic first row transition metals vs.group III salen complexes.Our predictive catalysis results show that the bite O-M-O angle plays an essential role in the catalysis.展开更多
A variety of unique Al(salen) complexes functionalized by imidazolium-based ionic liquid(IL) moieties with the salen ligand at the two sides of 3,3′-position have been successfully prepared, rather than familiar 5,5...A variety of unique Al(salen) complexes functionalized by imidazolium-based ionic liquid(IL) moieties with the salen ligand at the two sides of 3,3′-position have been successfully prepared, rather than familiar 5,5′-position reported previously.The catalytic activity obtained by these bifunctional catalysts could be superior to those of the binary type catalysts in the formation of five-membered heterocyclic compounds from the cycloaddition reaction of CO_2 and three-membered heterocyclic compounds(including terminal epoxides and N-substituted aziridines), presumably due to the distinguished intramolecularly synergistic catalysis, which might lead to perform the cycloaddition reaction at ambient conditions and retain excellent yield and unprecedented chemo-or regioselectivity. Moreover, the polyether-based trifunctional Al(salen) catalysts with the best catalytic performance could be regenerated and reused at least eight times without any obvious decreases in catalytic activity. Finally,the kinetic investigation suggested the structure of catalysts had important influences on the catalytic activity, thereby proposing the possible reaction mechanism.展开更多
Co-salen functionalized on graphene with an average pore size of 27.7 nm as a heterogeneous catalyst exhibited good catalytic activity and recyclability in cyclohexene oxidation.
SalenMX has drawn much attention recently,because it is nonsensitive to moisture and effective for copolymerization of CO2 and epoxides.However,usually expensive organic metal compounds were used.A low cost procedure ...SalenMX has drawn much attention recently,because it is nonsensitive to moisture and effective for copolymerization of CO2 and epoxides.However,usually expensive organic metal compounds were used.A low cost procedure of SalenMX preparation is described that SalenAl（OPr） can be obtained by using aluminium iso-propoxide reacted with SalenH2 in tetrahydrofuran at room temperature overnight.The catalyst precursor Schiff-base SalenH2 （N,N′-Bis（salicylidene）-1,2-phenylenediamine） was synthesized by refluxing 2 equiv salicylaldehyde and 1 equiv of 1,2-phenylendiamine in methnol for a period of time.SalenH2 and SalenAl（OPr） were characterized by FT-IR,mass Spectroscopy,UV-Vis and 1H-NMR.The copolymerization of carbon dioxide and cyclohexene oxide（CHO） was carried out at 80℃ for a certain period time using 50 mg SalenAl（OPr） as catalyst.SalenAl（OPr） had been shown to be an effective catalyst for the copolymerization of CO2 and CHO along with a small quantity of byproduct cyclic carbonate.The addition of various cocatalysts,including DMAP,N-MeIm,DBU and Bu4NCl or Bu4NBr salts can greatly enhance the rate of copolymerization.The copolymers were produced with >95% carbonate linkages and <5% cyclic carbonates.The highest catalytic efficiency is 190 g copolymer per g catalyst.展开更多
利用席佛碱催化体系催化二氧化碳(CO2)和环氧氯丙烷(ECH)共聚反应,合成出新型环状碳酸酯(ECHCO2)。利用红外光谱、核磁等方法对产物进行了表征。结果表明,最优化的试验温度是60℃,这一催化剂体系催化的活性高达920 polymer/(mol Co h),...利用席佛碱催化体系催化二氧化碳(CO2)和环氧氯丙烷(ECH)共聚反应,合成出新型环状碳酸酯(ECHCO2)。利用红外光谱、核磁等方法对产物进行了表征。结果表明,最优化的试验温度是60℃,这一催化剂体系催化的活性高达920 polymer/(mol Co h),并且有较高的选择性,高达99%。展开更多
文摘Located in the middle of the fever to solve the problem of CO_(2)emissions in the environment,CO_(2)sequestration by reaction with epoxides is one of the key tools,as it not only fixes CO_(2),but also makes it functional by leading to cyclic carbonates.Herein,the results are focused specifically on the formation of cyclic organic carbonates catalyzed by metal-salen complexes,previously achieved with yttrium and scandium,that are compared with those of analogous complexes containing metals from the first transition series,such as cobalt or chromium.Density functional theory(DFT)calculations allow to determine whether this switch of metals will be feasible and provide the basis for instigating future experimental efforts in this regard.The calculations analyzing the structure and electronics of the catalysts allow us to give not only a clear picture of whether these catalysts will be efficient,but also allow us to assess which metal center is the most convenient and/or whether the catalytic reaction will occur under mild conditions.Advanced buried volume calculations with the SambVca packages shed light on the different catalytic pockets of monometallic first row transition metals vs.group III salen complexes.Our predictive catalysis results show that the bite O-M-O angle plays an essential role in the catalysis.
基金supported by the National Science for Distinguished Young Scholars of China(21425627)the National Natural Science Foundation of China(21676306)+1 种基金the Natural Science Foundation of Guangdong Province(2016A030310211,2015A030313104)the Fundamental Research Funds for the Central Universities of Sun Yat-sen University
文摘A variety of unique Al(salen) complexes functionalized by imidazolium-based ionic liquid(IL) moieties with the salen ligand at the two sides of 3,3′-position have been successfully prepared, rather than familiar 5,5′-position reported previously.The catalytic activity obtained by these bifunctional catalysts could be superior to those of the binary type catalysts in the formation of five-membered heterocyclic compounds from the cycloaddition reaction of CO_2 and three-membered heterocyclic compounds(including terminal epoxides and N-substituted aziridines), presumably due to the distinguished intramolecularly synergistic catalysis, which might lead to perform the cycloaddition reaction at ambient conditions and retain excellent yield and unprecedented chemo-or regioselectivity. Moreover, the polyether-based trifunctional Al(salen) catalysts with the best catalytic performance could be regenerated and reused at least eight times without any obvious decreases in catalytic activity. Finally,the kinetic investigation suggested the structure of catalysts had important influences on the catalytic activity, thereby proposing the possible reaction mechanism.
基金the National Natural Science Foundation of China(20973079 and U1162201)Graduate Innovation Fund of Jilin University(20121051)
文摘Co-salen functionalized on graphene with an average pore size of 27.7 nm as a heterogeneous catalyst exhibited good catalytic activity and recyclability in cyclohexene oxidation.
文摘SalenMX has drawn much attention recently,because it is nonsensitive to moisture and effective for copolymerization of CO2 and epoxides.However,usually expensive organic metal compounds were used.A low cost procedure of SalenMX preparation is described that SalenAl（OPr） can be obtained by using aluminium iso-propoxide reacted with SalenH2 in tetrahydrofuran at room temperature overnight.The catalyst precursor Schiff-base SalenH2 （N,N′-Bis（salicylidene）-1,2-phenylenediamine） was synthesized by refluxing 2 equiv salicylaldehyde and 1 equiv of 1,2-phenylendiamine in methnol for a period of time.SalenH2 and SalenAl（OPr） were characterized by FT-IR,mass Spectroscopy,UV-Vis and 1H-NMR.The copolymerization of carbon dioxide and cyclohexene oxide（CHO） was carried out at 80℃ for a certain period time using 50 mg SalenAl（OPr） as catalyst.SalenAl（OPr） had been shown to be an effective catalyst for the copolymerization of CO2 and CHO along with a small quantity of byproduct cyclic carbonate.The addition of various cocatalysts,including DMAP,N-MeIm,DBU and Bu4NCl or Bu4NBr salts can greatly enhance the rate of copolymerization.The copolymers were produced with >95% carbonate linkages and <5% cyclic carbonates.The highest catalytic efficiency is 190 g copolymer per g catalyst.
基金supported by the National Natural Science Foundation of China (21676306,21425627)the National Key Research and Development Program of China (2016YFA0602900)the Natural Science Foundation of Guangdong Province (2016A030310211,2015A030313104)~~
