Since the concept of aromaticity was first introduced in transition metal complexes,metals have become a crucial component for modulating aromaticity,leading to a variety of structural frameworks.Initial studies succe...Since the concept of aromaticity was first introduced in transition metal complexes,metals have become a crucial component for modulating aromaticity,leading to a variety of structural frameworks.Initial studies successfully achieved aromatic pentalene dianions through metal-ion coordination,and recent advancements in bridgehead metallapentalenes have demonstrated the transformation of antiaromaticity into aromaticity.This research introduces an efficient[2+2+1]cycloaddition strategy with a dual-path cooperative mechanism for constructing the first structurally defined non-aromatic wingtip metallapentalene,including wingtip osmapentalene and its methoxy and hydroxy derivatives.Osmapentalenes display versatile reactivity,allowing for multi-site functionalization via nucleophilic and electrophilic substitutions.Furthermore,the hydroxy derivative easily undergoes a ring-opening reaction with methanol to form osmafuran.The lowest-energy absorption of wingtip osmapentalene falls within the visible range,with adjustable optical and electrochemical properties.展开更多
基金the National Natural Science Foundation of China(22175069 and 21772054).
文摘Since the concept of aromaticity was first introduced in transition metal complexes,metals have become a crucial component for modulating aromaticity,leading to a variety of structural frameworks.Initial studies successfully achieved aromatic pentalene dianions through metal-ion coordination,and recent advancements in bridgehead metallapentalenes have demonstrated the transformation of antiaromaticity into aromaticity.This research introduces an efficient[2+2+1]cycloaddition strategy with a dual-path cooperative mechanism for constructing the first structurally defined non-aromatic wingtip metallapentalene,including wingtip osmapentalene and its methoxy and hydroxy derivatives.Osmapentalenes display versatile reactivity,allowing for multi-site functionalization via nucleophilic and electrophilic substitutions.Furthermore,the hydroxy derivative easily undergoes a ring-opening reaction with methanol to form osmafuran.The lowest-energy absorption of wingtip osmapentalene falls within the visible range,with adjustable optical and electrochemical properties.
