Thorium
Mono- and Bis(imido) Complexes Made by Reprotonation
of <i>cyclo</i>-Metalated Amides
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Abstract
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″<sub>3</sub>] and K<sub>2</sub>[Th(NAr)<sub>2</sub>N″<sub>2</sub>], are readily made from insertion reactions
(Ar = aryl, N″ = N(SiMe<sub>3</sub>)<sub>2</sub>) into the
Th–C bond of the cyclometalated thorium amides [ThN″<sub>2</sub>(N(SiMe<sub>3</sub>)(SiMe<sub>2</sub>CH<sub>2</sub>))] and
K[ThN″(N(SiMe<sub>3</sub>)(SiMe<sub>2</sub>CH<sub>2</sub>))<sub>2</sub>]. X-ray and computational structural analyses show a “transition-metal-like” <i>cis</i>-bis(imido) geometry and polarized ThN bonds
with twice the Wiberg bond order of the formally single Th–N
bond in the same molecule
