While the reductive coupling of two nitriles mediated by transition metals has been widely studied in the past ten years,the analogous process promoted by rare-earth metals remains elusive.Herein,we report the selecti...While the reductive coupling of two nitriles mediated by transition metals has been widely studied in the past ten years,the analogous process promoted by rare-earth metals remains elusive.Herein,we report the selective C–C coupling of two nitriles by rare-earth metal reduced naphthalene complexes to assem-ble the first authentic rare-earth diazametallacyclopentadienes.Mechanistic studies reveal that the reac-tion proceeds through the insertion–release–insertion sequence,which is different from the known oxi-dative cyclometallation process for transition metals.This provides an alternative mechanism for metal-mediated reductive coupling of two nitriles.Furthermore,reactivity investigation indicates that diazascan-dacyclopentadiene exhibits distinct 1,4-hydrogenation and insertion reactions toward H_(2),isothiocyanate,isocyanide,and W(CO)_(6) to give diversified rare-earth metallacycles.These results indicate that rare-earth diazametallacyclopentadienes present unique chemistry,which is different from that of group 4 diazametallacyclopentadienes.展开更多
基金supported by the National Key R&D Program of China(no.2021YFF0701600)the National Natural Science Foundation of China(no.21890721,22131001).
文摘While the reductive coupling of two nitriles mediated by transition metals has been widely studied in the past ten years,the analogous process promoted by rare-earth metals remains elusive.Herein,we report the selective C–C coupling of two nitriles by rare-earth metal reduced naphthalene complexes to assem-ble the first authentic rare-earth diazametallacyclopentadienes.Mechanistic studies reveal that the reac-tion proceeds through the insertion–release–insertion sequence,which is different from the known oxi-dative cyclometallation process for transition metals.This provides an alternative mechanism for metal-mediated reductive coupling of two nitriles.Furthermore,reactivity investigation indicates that diazascan-dacyclopentadiene exhibits distinct 1,4-hydrogenation and insertion reactions toward H_(2),isothiocyanate,isocyanide,and W(CO)_(6) to give diversified rare-earth metallacycles.These results indicate that rare-earth diazametallacyclopentadienes present unique chemistry,which is different from that of group 4 diazametallacyclopentadienes.
