Synthesis and structure of diamido ether uranium(IV) and thorium(IV) halide "ate" complexes and their conversion to salt-free bis(alkyl) complexes.
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]UCl2.1/2C7H8(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.
Jantunen
Kimberly C
KC
Department of Chemistry, Simon Fraser University, Burnaby, British Columbia, CanadaV5A 1S6.
Haftbaradaran
Farzad
F
Katz
Michael J
MJ
Batchelor
Raymond J
RJ
Schatte
Gabriele
G
Leznoff
Daniel B
DB
D002712:Chlorides / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003958:Diamide / Q000737:chemistry*; D004987:Ethers / Q000737:chemistry*; D008024:Ligands; D008094:Lithium / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D013696:Temperature; D013910:Thorium / Q000737:chemistry*; D014501:Uranium / Q000737:chemistry*
D002712:Chlorides; D004987:Ethers; D008024:Ligands; D009942:Organometallic Compounds; D003958:Diamide; D014501:Uranium; D013910:Thorium; D008094:Lithium