Vinylidene and its heavier analogues are fundamentally important in synthetic chemistry,but their stabilization and structural characterization remains extremely challenging.Herein we describe that the reduction of an...Vinylidene and its heavier analogues are fundamentally important in synthetic chemistry,but their stabilization and structural characterization remains extremely challenging.Herein we describe that the reduction of an NHSi-stabilized stannyl-stannylene(2)with one molar equivalent of[(^(Mes)Nacnac)Mg]_(2)affords an NHSi-stabilized distannavinylidene(3).Single-crystal X-ray crystallography and density functional theory(DFT)calculations show that compound 3 features a pronounced Sn=Sn double bond and one lone pair of electrons at the two-coordinate Sn atom.Most strikingly,3 undergoes an interconversion with distannyne(4)upon the addition and removal of one molar equivalent of N-heterocyclic carbene.Compound 3 readily reacts with Ph_(2)C=C=O,Ad C≡P and(Al Cp^(*))_(4)to give the structurally interesting stannacycles(5,6)and an aluminyl distannyne(7),demonstrating its unique reactivity derived from the high substituent lability.展开更多
基金supported by the National Natural Science Foundation of China(22071124,22371130,22221002)the Frontiers Science Center for New Organic Matter at Nankai University(C029215001)+1 种基金the Fundamental Research Funds for the Central Universities(63206007)the Nankai University and Young Elite Scientists Sponsorship Program by Tianjin。
文摘Vinylidene and its heavier analogues are fundamentally important in synthetic chemistry,but their stabilization and structural characterization remains extremely challenging.Herein we describe that the reduction of an NHSi-stabilized stannyl-stannylene(2)with one molar equivalent of[(^(Mes)Nacnac)Mg]_(2)affords an NHSi-stabilized distannavinylidene(3).Single-crystal X-ray crystallography and density functional theory(DFT)calculations show that compound 3 features a pronounced Sn=Sn double bond and one lone pair of electrons at the two-coordinate Sn atom.Most strikingly,3 undergoes an interconversion with distannyne(4)upon the addition and removal of one molar equivalent of N-heterocyclic carbene.Compound 3 readily reacts with Ph_(2)C=C=O,Ad C≡P and(Al Cp^(*))_(4)to give the structurally interesting stannacycles(5,6)and an aluminyl distannyne(7),demonstrating its unique reactivity derived from the high substituent lability.
