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
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.
