Thorium Mono- and Bis(imido) Complexes Made by Reprotonation of cyclo-Metalated Amides
Thorium Mono- and Bis(imido) Complexes Made by Reprotonation of cyclo-Metalated Amides
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DOI：
10.1021/jacs.5b06630
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发表时间：
2015-08-26
影响因子：
15
通讯作者：
Arnold, Polly L.
中科院分区：
文献类型：
--
作者：
Bell, Nicola L.;Maron, Laurent;Arnold, Polly L.
Molecules containing actinide nitrogen multiple bonds are of current interest as simple models for new actinide nitride nuclear fuels, and for their potential for the catalytic activation of inert hydrocarbon C-H bonds. Complexes with up to three uranium nitrogen double bonds are now being widely studied, yet those with one thorium nitrogen double bond are rare, and those with two are unknown. A new, simple mono(imido) thorium complex and the first bis(imido) thorium complex, K[Th(=NAr)N"(3)] and 1(2[Th(= NAr)(2)N"(2)], are readily made from insertion reactions (Ar = aryl, N" = N(SiMe3)(2)) into the Th-C bond of the cyclometalated thorium amides [ThN"(2)(N(SiMe3)-(SiMe2CH2))] and K[ThN"(N(SiMe3)(SiMe2CH2))(2)]. X-ray and computational structural analyses show a "transition-metal-like" cis-bis(imido) geometry and polarized Th=N bonds with twice the Wiberg bond order of the formally single Th N-bond in the same molecule.
