The mechanism of cycloaddition reaction between singlet silylene carbene and acetone has been investigated with CCSD（T）//MP2/6-31G method. From the potential energy profile, it can be predicted that the reaction has...The mechanism of cycloaddition reaction between singlet silylene carbene and acetone has been investigated with CCSD（T）//MP2/6-31G method. From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. One consists of two steps： （1） the two reactants （R1, R2） firstly form a four-membered ring intermediate （INT4） through a barrier-free exothermic reaction of 585.9 kJ/mol; （2） Then intermediate （INT4） isomerizes to CH3-transfer product （P4.1） via a transition state （TS4.1） with energy barrier of 5.3 kJ/mol. The other is as follows： on the basis of intermediate （INT4） created between R1 and R2, intermediate （INT4） further reacts with acetone （R2） to form the intermediate （INT5） through a barrier-free exothermic reaction of 166.3 kJ/mol; Then, intermediate （INT5） isomerizes to a silicic bis-heterocyclic product （P5） via a transition state （TS5）, for which the barrier is 54.9 kJ/mol. The presented rule of this reaction： the [2＋2] cycloaddition effect between the π orbital of silylene carbene and the π orbital of π-bonded compounds leads to the formation of a four-membered ring intermediate （INT4）; The unsaturated property of C atom from carbene in the four-membered ring intermediate （INT4） results in the generation of CH3-transfer product （P4.1） and silicic bis-heterocyclic compound （P5）.展开更多
Reaction of a N-heterocycliccarbene（NHC） containing an anthracene unit and two N-picolyl moieties with Hg（OAc）2 yielded a novel mercury（Ⅱ） complex（1）. X-ray studies, UV-vis and fluorescence spectroscopy confi...Reaction of a N-heterocycliccarbene（NHC） containing an anthracene unit and two N-picolyl moieties with Hg（OAc）2 yielded a novel mercury（Ⅱ） complex（1）. X-ray studies, UV-vis and fluorescence spectroscopy confirmed that a strong interaction exists between the mercury atom and anthracene unit.展开更多
Herein,the origin of the diastereoselectivity of N-heterocyclic carbene(NHC)-catalyzed cross-benzoin reactions between an a-amino aldehyde and furfural was studied by density functional theory.The computational result...Herein,the origin of the diastereoselectivity of N-heterocyclic carbene(NHC)-catalyzed cross-benzoin reactions between an a-amino aldehyde and furfural was studied by density functional theory.The computational results showed that the reaction proceeded through four steps:nucleophilic addition of NHC onto furfural,formation of a Breslow intermediate,cross-coupling reaction between Breslow intermediate and a-amino alde hyde,and dissociation of the catalyst.The cross-coupling was identified as the diaste reoselectivity-determining step,with the R-configured product generated preferentially.Noncovalent inte raction(NCI)analysis showed that the C-H…O and C-H…F inte ractions were responsible for determining the diastereoselectivity.展开更多
Main observation and conclusion Two bis-imidazolium salts LH_(2)·Cl_(2) and LH_(2)·(PF_(6))_(2) with acylated piperazine linker and two N-heterocyclic carbene(NHC)silver(Ⅰ)and palladium(Ⅱ)complexes[L_(2)Ag...Main observation and conclusion Two bis-imidazolium salts LH_(2)·Cl_(2) and LH_(2)·(PF_(6))_(2) with acylated piperazine linker and two N-heterocyclic carbene(NHC)silver(Ⅰ)and palladium(Ⅱ)complexes[L_(2)Ag_(2)](PF_(6))_(2)(1)and[L_(2)Pd_(2)Cl_(4)](2)were prepared.The crystal structures of LH_(2)·Cl_(2) and 1 were confirmed by X-ray analysis.In 1,one 26-membered macrometallocycle was generated through two silver(Ⅰ)ions and two bidentate ligands L.The catalytic activity of 2 was investigated in Sonogashira,Heck-Mizoroki and Suzuki-Miyaura reactions.The results displayed that these C-C coupling reactions can be smoothly carried out under the catalysis of 2.展开更多
The transformation of β-carbine to diamond was studied by FTIR and XRD.The results indicated that the transformation was achieved with the pressure of 0.45MPa and temperature of 400 ℃.In the process,catalyst and dia...The transformation of β-carbine to diamond was studied by FTIR and XRD.The results indicated that the transformation was achieved with the pressure of 0.45MPa and temperature of 400 ℃.In the process,catalyst and diamond-crystal seeds were needless.展开更多
文摘The mechanism of cycloaddition reaction between singlet silylene carbene and acetone has been investigated with CCSD（T）//MP2/6-31G method. From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. One consists of two steps： （1） the two reactants （R1, R2） firstly form a four-membered ring intermediate （INT4） through a barrier-free exothermic reaction of 585.9 kJ/mol; （2） Then intermediate （INT4） isomerizes to CH3-transfer product （P4.1） via a transition state （TS4.1） with energy barrier of 5.3 kJ/mol. The other is as follows： on the basis of intermediate （INT4） created between R1 and R2, intermediate （INT4） further reacts with acetone （R2） to form the intermediate （INT5） through a barrier-free exothermic reaction of 166.3 kJ/mol; Then, intermediate （INT5） isomerizes to a silicic bis-heterocyclic product （P5） via a transition state （TS5）, for which the barrier is 54.9 kJ/mol. The presented rule of this reaction： the [2＋2] cycloaddition effect between the π orbital of silylene carbene and the π orbital of π-bonded compounds leads to the formation of a four-membered ring intermediate （INT4）; The unsaturated property of C atom from carbene in the four-membered ring intermediate （INT4） results in the generation of CH3-transfer product （P4.1） and silicic bis-heterocyclic compound （P5）.
基金supported by the Natural Science Foundation of Anhui Province(11040606M35)the Fundamental Research Funds for the Central Universities(JZ2014HGBZ0075)
文摘Reaction of a N-heterocycliccarbene（NHC） containing an anthracene unit and two N-picolyl moieties with Hg（OAc）2 yielded a novel mercury（Ⅱ） complex（1）. X-ray studies, UV-vis and fluorescence spectroscopy confirmed that a strong interaction exists between the mercury atom and anthracene unit.
基金financial support from the National Science Foundation of China(Nos.21822303 and 21772020)Startup Fund of Zhengzhou University of Light Industry(No.2017BSJJ036)。
文摘Herein,the origin of the diastereoselectivity of N-heterocyclic carbene(NHC)-catalyzed cross-benzoin reactions between an a-amino aldehyde and furfural was studied by density functional theory.The computational results showed that the reaction proceeded through four steps:nucleophilic addition of NHC onto furfural,formation of a Breslow intermediate,cross-coupling reaction between Breslow intermediate and a-amino alde hyde,and dissociation of the catalyst.The cross-coupling was identified as the diaste reoselectivity-determining step,with the R-configured product generated preferentially.Noncovalent inte raction(NCI)analysis showed that the C-H…O and C-H…F inte ractions were responsible for determining the diastereoselectivity.
基金the Tianjin Natural Science Foundation(No.18JCZDJC99600)the National Natural Science Foundation of China(No.21572159)the Program for Innovative Research Team in University of Tianjin(TD13-5074).
文摘Main observation and conclusion Two bis-imidazolium salts LH_(2)·Cl_(2) and LH_(2)·(PF_(6))_(2) with acylated piperazine linker and two N-heterocyclic carbene(NHC)silver(Ⅰ)and palladium(Ⅱ)complexes[L_(2)Ag_(2)](PF_(6))_(2)(1)and[L_(2)Pd_(2)Cl_(4)](2)were prepared.The crystal structures of LH_(2)·Cl_(2) and 1 were confirmed by X-ray analysis.In 1,one 26-membered macrometallocycle was generated through two silver(Ⅰ)ions and two bidentate ligands L.The catalytic activity of 2 was investigated in Sonogashira,Heck-Mizoroki and Suzuki-Miyaura reactions.The results displayed that these C-C coupling reactions can be smoothly carried out under the catalysis of 2.
文摘The transformation of β-carbine to diamond was studied by FTIR and XRD.The results indicated that the transformation was achieved with the pressure of 0.45MPa and temperature of 400 ℃.In the process,catalyst and diamond-crystal seeds were needless.
