A General and Modular Synthesis of Monoimidouranium(IV) Dihalides

• Published in: Inorganic chemistry 2011-05, Vol.50 (10), p.4235-4237
• Main Authors: Jilek, Robert. E, Spencer, Liam P, Kuiper, David L, Scott, Brian L, Williams, Ursula J, Kikkawa, James M, Schelter, Eric J, Boncella, James M
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic200377b

The conproportionation reaction between the dimeric diimidouranium(V) species [U(N t Bu)2(I)( t Bu2bpy)]2 ( t Bu2bpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) and UI3(THF)4 in the presence of additional t Bu2bpy yields U(N t Bu)(I)2( t Bu2bpy)(THF)2 (2), an unprecedented example of a monoimidouranium(IV) dihalide complex. The general synthesis of this family of uranium(IV) derivatives can be achieved more readily by adding 2 equiv of MN(H)R (M = Li, K; R = t Bu, 2,6- i PrC6H3, 2- t BuC6H4) to UX4 in the presence of coordinating Lewis bases to give complexes with the general formula U(NR)(X)2(L) n (X = Cl, I; L = t Bu2bpy, n = 1; L = THF, n = 2). The complexes were characterized by 1H NMR spectroscopy and single-crystal X-ray diffraction analysis of compounds 2 and {U[N(2,6- i PrC6H3)](Cl)2(THF)2}2 (4). (The X-ray structures of 5 and 6 are reported in the Supporting Information.)