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.
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