Reactivity of a triamidoamine complex of trivalent uranium

摘要

Reduction of [U(NN'_3)I][NN'_3 = N(CH_2CH_2NSiMe_2Bu~t)_3] with potassium in pentane gives the purple trivalent monomer [U(N_3)] in good yield, this compound having previously been synthesised via fractional vacuum sublimation of mixed-valent [{U(NN'_3)}_2(mu-Cl)]. The magnetic susceptibility of this compound is consistent with the presence of U(III) centres, and this is onfirmed by a charateristic near IR spectrum. Its reactions with Lewis bases to give e.g. [U(NN'_3)(Py)] and [U(NN'_3)(HMPA)] are reported, along with the molecular structure of the latter. The complex [U(NN'_3)] is readily oxidised, imido and hydrazido complexes being formed readily by reaction with trimethylsilyl-azide and -diazomethane, respectively. The reaction with methylene trimethylphosproane however led to the formation of an addition compound [U(NN'_3)(CH_2PMe_3)]. Reaction of this latter complex with air gave a few crystals of the unusual hydroxo complex [U(NN'_3)(OH)(CH_2PMe_3)] which was structurally characterised. Reaction of [U(NN'_3)(CH_2PMe_3)] with trimethylamine N-oxide gave pentavalent [U(NN'_3)(O)], or perhaps a dimer thereof. The latter complex reacted with [U(NN'_3)] to give the bridging oxo complex [{U(NN'_3)}_2(mu-O)] which could also be prepared directly by reaction of trimethylamine N-oxide with [U(NN'_3)].