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Issue 18, 2005
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Synthesis and structure of diamido ether uranium(iv) and thorium(iv) halide “ate” complexes and their conversion to salt-free bis(alkyl) complexes

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Abstract

The high-yield synthesis, spectroscopic and structural determination of three new uranium(IV) and thorium(IV) “ate” complexes supported by three different diamido ether ligands are reported. The reaction of Li2[2,6-iPr2PhN(CH2CH2)]2O (Li2[DIPPNCOCN]) with 1 equiv. of UCl4 in THF generates [DIPPNCOCN]UCl3Li(THF)2 (1), while reaction in toluene/ether gives salt-free [DIPPNCOCN]UCl2·½C7H8 (2), which was identified by paramagnetically shifted 1H NMR. Reaction of 0.5 equiv. of {[tBuNON]UCl2}2 ([tBuNON] = [(CH3)3CN(Si(CH3)2)]2O2−) with 3.5 equiv. LiI in toluene and a minimal amount of THF results in [tBuNON]UI3Li(THF)2 (3) and is very similar in structure to 1. {[MesNON]ThCl3Li(THF)}2 (4), a dimeric complex with a Th2Li2Cl6 core, is prepared by reaction of Li2[2,4,6-Me3PhN(Si(CH3)2)]2O (Li2[MesNON]) with ThCl4 in THF. The analogous reaction in toluene did not yield the salt-free complex but rather a sterically crowded diligated compound, [MesNON]2Th (5), which was also structurally characterized. Complex 5 was prepared rationally by reacting 2 equiv. Li2[MesNON] with ThCl4 in toluene. The reaction of 1 and 3 with 2 equiv. of LiCH2Si(CH3)3 generates the stable, salt-free organoactinides [DIPPNCOCN]U(CH2Si(CH3)3)2 (6) and [tBuNON]U(CH2Si(CH3)3)2 (7). Complex 6 was structurally characterized. These reactions illustrate the viability of “ate” complexes as useful synthetic precursors.

Graphical abstract: Synthesis and structure of diamido ether uranium(iv) and thorium(iv) halide “ate” complexes and their conversion to salt-free bis(alkyl) complexes

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Supplementary files

Article information


Submitted
03 May 2005
Accepted
05 Jul 2005
First published
03 Aug 2005

Dalton Trans., 2005, 3083-3091
Article type
Paper

Synthesis and structure of diamido ether uranium(IV) and thorium(IV) halide “ate” complexes and their conversion to salt-free bis(alkyl) complexes

K. C. Jantunen, F. Haftbaradaran, M. J. Katz, R. J. Batchelor, G. Schatte and D. B. Leznoff, Dalton Trans., 2005, 3083
DOI: 10.1039/B506180F

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