Metalla-isosilabenzenes and metalla-isogermabenzenes have been successfully synthesized by the formal[5+1]-cycloaddition of diethynylsilane or diethynylgermane with simple metal complexes.This is the first example of ...Metalla-isosilabenzenes and metalla-isogermabenzenes have been successfully synthesized by the formal[5+1]-cycloaddition of diethynylsilane or diethynylgermane with simple metal complexes.This is the first example of a heavier Group 14 metalla-isobenzene isomer bearing a cumulative double bond motif within a metallacycle.These novel complexes were fully characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis.The stabilization of the cyclic metal-vinylidene complexes has been analyzed using density functional theory(DFT)calculations.When the metalla-isosilabenzenes bearing Si—H bond were treated with the trityl salt as a hydride scavenger,the formation of silylium cation was observed spectroscopically.Both of metalla-isosilabenzenes and metalla-isogermabenzenes can readily undergo migratory insertion reactions to furnish siloles or germoles.展开更多
Chalcogenirenium cations,featuring an unsaturated three-membered organic ring,are limited but known to be synthesizable from alkynes with bulky electron-donating groups.Metalla-chalcogenirenium compounds have been syn...Chalcogenirenium cations,featuring an unsaturated three-membered organic ring,are limited but known to be synthesizable from alkynes with bulky electron-donating groups.Metalla-chalcogenirenium compounds have been synthesized as stable compounds through the reactions of a cyclic metal-carbyne complex-metallapentalyne with PhSCI,PhSeCI or PhTeCI.As a result of the high strain in the three-membered metallacycles,the metalla-chalcogenirenium cations react readily with the base or chloride ions.These reactions furnish a series of unprecedented chalcogenirenium cations with intact M=C bonds.The intrinsic stabilization effect of aromaticity is further elucidated by density functional calculations.展开更多
基金the National Natural Science Foundation of China(Grant No.22171234).
文摘Metalla-isosilabenzenes and metalla-isogermabenzenes have been successfully synthesized by the formal[5+1]-cycloaddition of diethynylsilane or diethynylgermane with simple metal complexes.This is the first example of a heavier Group 14 metalla-isobenzene isomer bearing a cumulative double bond motif within a metallacycle.These novel complexes were fully characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis.The stabilization of the cyclic metal-vinylidene complexes has been analyzed using density functional theory(DFT)calculations.When the metalla-isosilabenzenes bearing Si—H bond were treated with the trityl salt as a hydride scavenger,the formation of silylium cation was observed spectroscopically.Both of metalla-isosilabenzenes and metalla-isogermabenzenes can readily undergo migratory insertion reactions to furnish siloles or germoles.
基金the National Natural Science Foundation of China(Nos.U1705254,21871225,and 21931002)the Shenzhen Science and Technology Innovation Committee(No.JCYJ20200109140812302)+1 种基金the Fundamental Research Funds for the Central Universities(No.20720190042)We thank Dr.Liu Leo Liu for constructive criticism of the manuscript.
文摘Chalcogenirenium cations,featuring an unsaturated three-membered organic ring,are limited but known to be synthesizable from alkynes with bulky electron-donating groups.Metalla-chalcogenirenium compounds have been synthesized as stable compounds through the reactions of a cyclic metal-carbyne complex-metallapentalyne with PhSCI,PhSeCI or PhTeCI.As a result of the high strain in the three-membered metallacycles,the metalla-chalcogenirenium cations react readily with the base or chloride ions.These reactions furnish a series of unprecedented chalcogenirenium cations with intact M=C bonds.The intrinsic stabilization effect of aromaticity is further elucidated by density functional calculations.
