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Triamidoamine complexes of the actinides; from mixed-valence bimetallics to dinitrogen activation



Reduction of pale green {tris (tert-butyldimethylsilylamidoethyl) amino}chlorouranium(IV) [U(NN3')Cl] with potassium gives the purple mixed valence (III/IV) dimer [{U(NN3')}(2)-mu-Cl]. Although the two metal atoms in this compound are indistinguishable by X-ray crystallography, other data are consistent with the presence of distinct tri- and tetravalent centres. Careful fractional sublimation of this species allows the 'cracking' of the molecule into [U(NN3')Cl] and purple [U(NN3')]. This latter species reacts with dinitrogen gas to give reversible conversion to [{U(NN3')}(2)(mu(2)-eta(2):eta(2)-N-2)], the first dinitrogen complex of an actinide. The molecular structure as determined by X-ray crystallography shows that the dinitrogen ligand is side-on bonded to the two uranium centres and that the N-N bond length is essentially the same as that in free dinitrogen. This, and variable temperature magnetic data are consistent with the formulation of this compound as a simple Lewis base adduct of uranium(III). The preference for side-on over end-on bonding is explained on the basis that the dinitrogen pi(P) orbital is a better sigma-donor than the sigma(P), orbital to trivalent uranium. (C) 1998 Elsevier Science S.A

Topics: QD, TA, TN
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