title: Low-valent molecular plutonium halide complexes.
abstract: Treatment of plutonium metal with 1.5 equiv of bromine in tetrahydrofuran (thf) led to isolation of PuBr3(thf)4 (1), which is a new versatile synthon for exploration of non-aqueous Pu(III) chemistry. Adventitious water in the system resulted in structural characterization of the eight-coordinate complex [PuBr2(H2O)6][Br] (2). The crystal structure of PuI3(thf)4 (3) has been determined for the first time and is isostructural with UI3(thf)4. Attempts to form a bis(imido) plutonyl(VI) moiety ([Pu(NR)2](2+)) by oxidation of PuI3(py)4 with iodine and (t)BuNH2 resulted in crystallization of the Pu(III) complex [PuI2(thf)4(py)][I3] (4). Dissolution of a Pu(IV) carbonate with a HCl/Et2O solution in thf gave the mixed valent (III/IV) complex salt [PuCl2(thf)5][PuCl5(thf)] (5) as the only tractable product. Oxidation of Pu[N(SiMe3)2]3 with TeCl4 afforded the Pu(IV) complex Pu[N(SiMe3)2]3Cl (6), which may prove to be a useful entry route for investigation of organometallic/non-aqueous tetravalent plutonium chemistry.
authors: Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. gaunt@lanl.gov
authors: Andrew J
authors: AJ
authors: Gaunt
authors: Sean D
authors: SD
authors: Reilly
authors: Alejandro E
authors: AE
authors: Enriquez
authors: Trevor W
authors: TW
authors: Hayton
authors: James M
authors: JM
authors: Boncella
authors: Brian L
authors: BL
authors: Scott
authors: Mary P
authors: MP
authors: Neu