The title compounds were synthesized by taking advantage of the Martin ligand. Their structures were determined by X-ray crystallography. Pentacoordinate thiasiliranides were hydrolyzed to give the corresponding thiol...The title compounds were synthesized by taking advantage of the Martin ligand. Their structures were determined by X-ray crystallography. Pentacoordinate thiasiliranides were hydrolyzed to give the corresponding thiol. Pentacoordinate chalcogenaphosphiranes were found to have polar P-chalcogen bonds, which were confirmed by their reactions with CF3SO3Me to give the corresponding 1-（methylchalcogena）alkylphosphonium triflates and by the solvent-dependent NMR studies.展开更多
Three-membered cyclic compounds are a fascinating class of compounds:they have the maximum torsional and angular strain(sp^(3)hybridization but bond angles deviate from 109°28’),and possess unique physical and c...Three-membered cyclic compounds are a fascinating class of compounds:they have the maximum torsional and angular strain(sp^(3)hybridization but bond angles deviate from 109°28’),and possess unique physical and chemical properties.A lot of effort has been devoted to their synthesis and applications in recent years.This review provides an overview of various synthesis strategies for three-membered cyclic compounds,and summarizes the proposed reaction mechanisms and key issues such as structure-property relationships through specific examples.Meanwhile,the advantages and disadvantages of different synthesis strategies were discussed,including the recently developed electrochemical synthesis methods.Finally,the prospects and challenges for further scientific research and practical applications of three-membered cyclic compounds were emphasized.The summary of three-membered cyclic compounds is beneficial for the development and utilization of novel functionalized molecules.展开更多
The structures of silylenoid H_2SiLiCl have been studied by RHF/3-21G gradient method. Three equilibrium states and two isomerization transition states are located. The electronic energy, Mulliken populations, dipole ...The structures of silylenoid H_2SiLiCl have been studied by RHF/3-21G gradient method. Three equilibrium states and two isomerization transition states are located. The electronic energy, Mulliken populations, dipole moments and frontier molecular orbitals (FMO) of every structure and the isomeric barriers are also given and analyzed. Further single point calculations on the 3-21G optimum geometries were performed using 6-21G basis set. The calculations show that three-membered ring structure of H_2SiLiCl is the most stable and detectable, and the 'classical' tetrahedral form is not the local minimum on the potential energy surface.展开更多
The structural characteristics of silylenoids, H2SiMX, where M = Li or Na and X = F or Cl, have been studied by ab initio calculations. H2SiMX can be represented as adducts of silylene H2Si with alkali metal halogenid...The structural characteristics of silylenoids, H2SiMX, where M = Li or Na and X = F or Cl, have been studied by ab initio calculations. H2SiMX can be represented as adducts of silylene H2Si with alkali metal halogenides, MX. The associative energies at different calculational levels of various structures of H2SiMX are given. Effects of metallic and haloid atoms on the stability of various structures of H2SiMX are also discussed in this paper.展开更多
ALTHOLIGH carbenoids as the active organometallic intermediates have been widely used in organic syntheses, up to now, only few simple saturated and unsaturated carbenoids, such as H<sub>2</sub>CLiF, Cl<...ALTHOLIGH carbenoids as the active organometallic intermediates have been widely used in organic syntheses, up to now, only few simple saturated and unsaturated carbenoids, such as H<sub>2</sub>CLiF, Cl<sub>3</sub>CLi, HCLiF<sub>2</sub> and HCCLiF, have been studied by theoretical methods.展开更多
文摘The title compounds were synthesized by taking advantage of the Martin ligand. Their structures were determined by X-ray crystallography. Pentacoordinate thiasiliranides were hydrolyzed to give the corresponding thiol. Pentacoordinate chalcogenaphosphiranes were found to have polar P-chalcogen bonds, which were confirmed by their reactions with CF3SO3Me to give the corresponding 1-（methylchalcogena）alkylphosphonium triflates and by the solvent-dependent NMR studies.
基金supported by the National Natural Science Foundation of China(Nos.U21A20307,22178359,and 22308087)CAS Project for Young Scientists in Basic Research(No.YSBR-052).
文摘Three-membered cyclic compounds are a fascinating class of compounds:they have the maximum torsional and angular strain(sp^(3)hybridization but bond angles deviate from 109°28’),and possess unique physical and chemical properties.A lot of effort has been devoted to their synthesis and applications in recent years.This review provides an overview of various synthesis strategies for three-membered cyclic compounds,and summarizes the proposed reaction mechanisms and key issues such as structure-property relationships through specific examples.Meanwhile,the advantages and disadvantages of different synthesis strategies were discussed,including the recently developed electrochemical synthesis methods.Finally,the prospects and challenges for further scientific research and practical applications of three-membered cyclic compounds were emphasized.The summary of three-membered cyclic compounds is beneficial for the development and utilization of novel functionalized molecules.
文摘The structures of silylenoid H_2SiLiCl have been studied by RHF/3-21G gradient method. Three equilibrium states and two isomerization transition states are located. The electronic energy, Mulliken populations, dipole moments and frontier molecular orbitals (FMO) of every structure and the isomeric barriers are also given and analyzed. Further single point calculations on the 3-21G optimum geometries were performed using 6-21G basis set. The calculations show that three-membered ring structure of H_2SiLiCl is the most stable and detectable, and the 'classical' tetrahedral form is not the local minimum on the potential energy surface.
基金supported by the National Natural Science Fundation of China.
文摘The structural characteristics of silylenoids, H2SiMX, where M = Li or Na and X = F or Cl, have been studied by ab initio calculations. H2SiMX can be represented as adducts of silylene H2Si with alkali metal halogenides, MX. The associative energies at different calculational levels of various structures of H2SiMX are given. Effects of metallic and haloid atoms on the stability of various structures of H2SiMX are also discussed in this paper.
文摘ALTHOLIGH carbenoids as the active organometallic intermediates have been widely used in organic syntheses, up to now, only few simple saturated and unsaturated carbenoids, such as H<sub>2</sub>CLiF, Cl<sub>3</sub>CLi, HCLiF<sub>2</sub> and HCCLiF, have been studied by theoretical methods.
