Carbon nitride (CN) in CN encapsulated Ni/ Al2O3 (denoted as CN/Ni/Al2O3) catalyst was evidenced previously as a material in electron-rich state and possessed H-2-dissociative adsorption activity due to the electron d...Carbon nitride (CN) in CN encapsulated Ni/ Al2O3 (denoted as CN/Ni/Al2O3) catalyst was evidenced previously as a material in electron-rich state and possessed H-2-dissociative adsorption activity due to the electron doping effect from underlying nickel. In this report, iron oxide loaded on the CN/Ni/Al2O3 was synthesized and investigated by Fischer-Tropsch (F-T) synthesis to test the special effect of electron-rich support on the catalytic activity of iron oxide. The Fe/CN/Al2O3 and CN/Ni/Al2O3 samples were accordingly synthesized for comparison. In Fe/CN/Ni/Al2O3, the iron oxide was reduced to magnetite by syngas as evidenced by the in-situ XPS measurements and XRD pattern of used catalyst. Compared with Fe/CN/Al2O3, more light hydrocarbons over Fe/CN/Ni/Al2O3 were observed. It should be understood by the interaction between iron oxide and support mainly due to the effect of electron-rich state and thus enhanced H-2 adsorption ability. In addition, such a novel support facilitated the CO conversion and retarded the water-gas shift reaction and CO2 formation. The new type of adjustment on electronic state should be useful for novel catalyst design. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.展开更多
The ground state spins coupled through electron-rich rings of bicarbenes and binitreneshave been studied at UHF/6-31G* level. The results demonstrate that ferromagnetic couplingexists in these molecules, and electron-...The ground state spins coupled through electron-rich rings of bicarbenes and binitreneshave been studied at UHF/6-31G* level. The results demonstrate that ferromagnetic couplingexists in these molecules, and electron-rich rings are the potential ferromagnetic coupling units.展开更多
The characters of coupling between two doublet NO radicals linked through electron-rich rings have been studied. The results demonstrate that the molecules have triplet ground states, and ferromagnetic coupling exists...The characters of coupling between two doublet NO radicals linked through electron-rich rings have been studied. The results demonstrate that the molecules have triplet ground states, and ferromagnetic coupling exists in these molecules.展开更多
The arylation of C(sp^(3))-H bonds has been a priority research topic in organic synthesis.Minsici reactions have been the powerful methods for C(sp^(3))-C(sp^(2))bonds formation.Despite its mature development,the sco...The arylation of C(sp^(3))-H bonds has been a priority research topic in organic synthesis.Minsici reactions have been the powerful methods for C(sp^(3))-C(sp^(2))bonds formation.Despite its mature development,the scopes of arenes are usually suitable for elec-tron-deficient heterocyclic compounds,rather than electron-rich arenes.Herein,we report an electrooxidation-induced alkylation of electron-rich arenes with H_(2) evolution under exogenous oxidant-free conditions,avoiding the utilization of metal catalysts.This pro-tocol is well performed with various electron-rich aniline derivatives and nitrogen-containing heterocyclic compounds.We anticipate that this electro-oxidative C(sp^(3))-H arylation represents an important expansion for the classic arenes alkylation,thereby proving an attractive strategy for the developments of radical cross-coupling chemistry.展开更多
The application ot the sulfinatodehalogenation reaction system for the perfluoroalkylation of electron-rich aromatics is further studied.It was shown that perfluoroalkyl iodides reacted with polyhydric phenols,N,N-dia...The application ot the sulfinatodehalogenation reaction system for the perfluoroalkylation of electron-rich aromatics is further studied.It was shown that perfluoroalkyl iodides reacted with polyhydric phenols,N,N-dialkylanilines,2,5-dimethylpyrrole,N-methylpyrrole initiated by Na_2S_2O_4- NaHCO_3 gave the corresponding perfluoroalkylated products in moderate to good yields.展开更多
A series of V-type chromophores with electron-rich heterocyclevinylene bridges have been synthesized via Wittig-Horner-Emmons and Vilsmeier reactions.All the target chromophores showed strong one-photon and two-photon...A series of V-type chromophores with electron-rich heterocyclevinylene bridges have been synthesized via Wittig-Horner-Emmons and Vilsmeier reactions.All the target chromophores showed strong one-photon and two-photon excited emission,and their electron properties could be tuned by using different heterocycles such as furan,thiophene and pyrrole moieties in I-III.The maximum two-photon absorption (TPA) cross sections occurred at 760 nm and were measured to be in the range of 400-800 GM.展开更多
基金supported by the Ministry of Science and Technology of China (2009CB623504)the National Science Foundation of China (20673054,21273107)Sinopec Shanghai Research Institute of Petrochemical Technology
文摘Carbon nitride (CN) in CN encapsulated Ni/ Al2O3 (denoted as CN/Ni/Al2O3) catalyst was evidenced previously as a material in electron-rich state and possessed H-2-dissociative adsorption activity due to the electron doping effect from underlying nickel. In this report, iron oxide loaded on the CN/Ni/Al2O3 was synthesized and investigated by Fischer-Tropsch (F-T) synthesis to test the special effect of electron-rich support on the catalytic activity of iron oxide. The Fe/CN/Al2O3 and CN/Ni/Al2O3 samples were accordingly synthesized for comparison. In Fe/CN/Ni/Al2O3, the iron oxide was reduced to magnetite by syngas as evidenced by the in-situ XPS measurements and XRD pattern of used catalyst. Compared with Fe/CN/Al2O3, more light hydrocarbons over Fe/CN/Ni/Al2O3 were observed. It should be understood by the interaction between iron oxide and support mainly due to the effect of electron-rich state and thus enhanced H-2 adsorption ability. In addition, such a novel support facilitated the CO conversion and retarded the water-gas shift reaction and CO2 formation. The new type of adjustment on electronic state should be useful for novel catalyst design. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
文摘The ground state spins coupled through electron-rich rings of bicarbenes and binitreneshave been studied at UHF/6-31G* level. The results demonstrate that ferromagnetic couplingexists in these molecules, and electron-rich rings are the potential ferromagnetic coupling units.
文摘The characters of coupling between two doublet NO radicals linked through electron-rich rings have been studied. The results demonstrate that the molecules have triplet ground states, and ferromagnetic coupling exists in these molecules.
基金the National Key R&D Program of China(No.2021YFA1500104)the National Natural Science Foundation of China(No.22031008)the Science Foundation of Wuhan(No.2020010601012192)。
文摘The arylation of C(sp^(3))-H bonds has been a priority research topic in organic synthesis.Minsici reactions have been the powerful methods for C(sp^(3))-C(sp^(2))bonds formation.Despite its mature development,the scopes of arenes are usually suitable for elec-tron-deficient heterocyclic compounds,rather than electron-rich arenes.Herein,we report an electrooxidation-induced alkylation of electron-rich arenes with H_(2) evolution under exogenous oxidant-free conditions,avoiding the utilization of metal catalysts.This pro-tocol is well performed with various electron-rich aniline derivatives and nitrogen-containing heterocyclic compounds.We anticipate that this electro-oxidative C(sp^(3))-H arylation represents an important expansion for the classic arenes alkylation,thereby proving an attractive strategy for the developments of radical cross-coupling chemistry.
基金the National Natural Science Foundation of China.Part ⅩⅩⅢ in this series,see Huang,W.-Y.Zhuang,J.-L.,Chinese J.Chem.,9,270 (1991).
文摘The application ot the sulfinatodehalogenation reaction system for the perfluoroalkylation of electron-rich aromatics is further studied.It was shown that perfluoroalkyl iodides reacted with polyhydric phenols,N,N-dialkylanilines,2,5-dimethylpyrrole,N-methylpyrrole initiated by Na_2S_2O_4- NaHCO_3 gave the corresponding perfluoroalkylated products in moderate to good yields.
基金the National Natural Science Foundation of China (21002075 and 21034006) for financial support
文摘A series of V-type chromophores with electron-rich heterocyclevinylene bridges have been synthesized via Wittig-Horner-Emmons and Vilsmeier reactions.All the target chromophores showed strong one-photon and two-photon excited emission,and their electron properties could be tuned by using different heterocycles such as furan,thiophene and pyrrole moieties in I-III.The maximum two-photon absorption (TPA) cross sections occurred at 760 nm and were measured to be in the range of 400-800 GM.
