Thorium Mono- and Bis(imido) Complexes Made by Reprotonation of cyclo-Metalated Amides

摘要: Molecules containing actinide–nitrogen multiple bonds are of current interest as simple models for new actinide nitride nuclear fuels, and their potential the catalytic activation inert hydrocarbon C–H bonds. Complexes with up to three uranium–nitrogen double now being widely studied, yet those one thorium–nitrogen bond rare, two unknown. A new, mono(imido) thorium complex first bis(imido) complex, K[Th(═NAr)N″3] K2[Th(═NAr)2N″2], readily made from insertion reactions (Ar = aryl, N″ N(SiMe3)2) into Th–C cyclometalated amides [ThN″2(N(SiMe3)(SiMe2CH2))] K[ThN″(N(SiMe3)(SiMe2CH2))2]. X-ray computational structural analyses show a “transition-metal-like” cis-bis(imido) geometry polarized Th═N twice Wiberg order formally single Th–N in same molecule.