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Triamidoamine complexes of the actinides; from mixed-valence bimetallics to dinitrogen activation
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UNSPECIFIED (1998) Triamidoamine complexes of the actinides; from mixed-valence bimetallics to dinitrogen activation. In: Actinides-97 Conference, BADEN BADEN, GERMANY, SEP 21-26, 1997. Published in: JOURNAL OF ALLOYS AND COMPOUNDS, 271 pp. 150-153. ISSN 0925-8388.
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Abstract
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.
Item Type: | Conference Item (UNSPECIFIED) | ||||
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Subjects: | Q Science > QD Chemistry T Technology > TA Engineering (General). Civil engineering (General) T Technology > TN Mining engineering. Metallurgy |
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Journal or Publication Title: | JOURNAL OF ALLOYS AND COMPOUNDS | ||||
Publisher: | ELSEVIER SCIENCE SA | ||||
ISSN: | 0925-8388 | ||||
Official Date: | 12 June 1998 | ||||
Dates: |
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Volume: | 271 | ||||
Number of Pages: | 4 | ||||
Page Range: | pp. 150-153 | ||||
Publication Status: | Published | ||||
Title of Event: | Actinides-97 Conference | ||||
Location of Event: | BADEN BADEN, GERMANY | ||||
Date(s) of Event: | SEP 21-26, 1997 |
Data sourced from Thomson Reuters' Web of Knowledge
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