2013
DOI: 10.1021/ic4009812
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“Oxidative Addition” of Halogens to Uranium(IV) Bis(amidophenolate) Complexes

Abstract: A series of U(IV) complexes, ((R)ap)2U(THF)2 [R = tert-butyl (t-Bu) (1), adamantyl (Ad) (2), diisopropylphenyl (dipp) (3)], supported by the redox-active 4,6-di-tert-butyl-2-(R)amidophenolate ligand, have been synthesized by salt metathesis of 2 equiv of the alkali metal salt of the ligand, M2[(R)ap] [M = K (1 and 2), Na (3)], with UCl4. Exposure of these uranium complexes to 1 equiv of PhICl2 results in oxidative addition to uranium, forming the bis-(4,6-di-tert-butyl-2-(R)iminosemiquinone) ([(R)isq](1-)) ura… Show more

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Cited by 40 publications
(33 citation statements)
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“…The uranium(IV) bis(amidophenolate) complexes ( R ap) 2 U(THF) 2 (R = t-butyl, adamantyl) bind halogens via "oxidative addition" induced by the amidophenolate ligands to afford the corresponding uranium(IV) iminobenzosemiquinone radical complexes [( R isq) 2 UCl] 2 ( 2 -Cl) 2 [372]. The radical ligand was confirmed by both electronic absorption spectra that show the characteristic -* transitions between 700 and 800 nm for the open-shell, iminosemiquinone ligand, and by X-ray crystallography, which revealed the expected bond distortions for a radical species.…”
Section: Radical-containing Uranium Complexesmentioning
confidence: 99%
“…The uranium(IV) bis(amidophenolate) complexes ( R ap) 2 U(THF) 2 (R = t-butyl, adamantyl) bind halogens via "oxidative addition" induced by the amidophenolate ligands to afford the corresponding uranium(IV) iminobenzosemiquinone radical complexes [( R isq) 2 UCl] 2 ( 2 -Cl) 2 [372]. The radical ligand was confirmed by both electronic absorption spectra that show the characteristic -* transitions between 700 and 800 nm for the open-shell, iminosemiquinone ligand, and by X-ray crystallography, which revealed the expected bond distortions for a radical species.…”
Section: Radical-containing Uranium Complexesmentioning
confidence: 99%
“…The U(IV) bis-amidophenolate compounds (series 26) were synthesised from salt elimination between UCl 4 and the ligand bis-alkali metal salt. 37 Compound series 26 were treated with PhICl 2 or I 2 , resulting in the appearance of formal oxidative addition by the halogens (Scheme 18). However, the uranium oxidation states in the reactants and products are all the same (+4), while the ligands were oxidised from L 2− (in series 26) to L 1− (series 27 and 28) and so these reactions are not true type (a) oxidative additions.…”
Section: Oxidative Addition Involving Redox Non-innocent Ligands or Omentioning
confidence: 99%
“…The DOPO class of ligands is related to the iminoquinone ( R iq)/iminosemiquinone ( R isq)/amidophenolate ( R ap) (iq = 4,6-di-tert-butyl-2-[(R)-iminoquinone]; ap = 4,6-di-tert-butyl-2-[(R)-amidophenolate]; R = t Bu, Ad, dipp; Ad = 1-adamantyl, dipp =2,6-diisopropylphenyl) family, which has recently been used to perform multielectron oxidative addition 9 and reductive elimination on uranium. 10 For instance, the bidentate amidophenolate ligands in ( R ap) 2 U(THF) 2 can mediate oxidative addition of chlorine or iodine at monomeric U(IV) complexes, where the two reducing equivalents necessary for bond cleavage are derived from the ligand.…”
Section: ■ Introductionmentioning
confidence: 99%
“…Thus, radical iminosemiquinone ligands ( R isq) support the products from oxidative addition, which are dimeric, [( R isq) 2 UCl] 2 (μ-Cl) 2 , and monomeric, ( R isq) 2 UI 2 . 9 Alternately, radical reductive elimination of bibenzyl occurs from tetrabenzyluranium using the iminoquinone form of the ligand. These are subsequently reduced to generate the corresponding amidophenolate uranium dialkyls, ( R ap)U(CH 2 Ph) 2 .…”
Section: ■ Introductionmentioning
confidence: 99%