A dinuclear Eu(III) complex Eu2(OCH2NMe2)2[N(SiMe3)2]4 (1) was synthesized via the reaction of Me3NO and Eu[N(SiMe3)2]3, during which the unprecedented C–H activation of Me3NO occurred along with oxygen-atom transfer. A simple Eu[N(SiMe3)2]3(OPMe3) adduct (2) was obtained when Me3PO was used, which should be due to the higher energy barrier and poorer product stability that prevent the formation of the phosphine substituted analogue of 1.
