title: "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-)) uranium(IV) dichloride dimer, [((R)isq)2UCl]2(μ(2)-Cl)2 [R = t-Bu (4), Ad (5), dipp (6)]. The addition of iodine to 1 forms ((tBu)isq)2UI2(THF) (7), while the reactivity of I2 with 2 and 3 results in decomposition. Complexes 1-7 have been characterized by (1)H NMR and electronic absorption spectroscopies. X-ray crystallography was employed to elucidate structural parameters of 2, 3, 5, and 7.
authors.affiliation: H. C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
authors.forename: Ellen M
authors.initials: EM
authors.lastname: Matson
authors.forename: Stacey R
authors.initials: SR
authors.lastname: Opperwall
authors.forename: Phillip E
authors.initials: PE
authors.lastname: Fanwick
authors.forename: Suzanne C
authors.initials: SC
authors.lastname: Bart