Low-Valent Molecular Plutonium Halide Complexes

• Published in: Inorganic chemistry Vol. 47; no. 18; pp. 8412 - 8419
• Main Authors: Gaunt, Andrew J, Reilly, Sean D, Enriquez, Alejandro E, Hayton, Trevor W, Boncella, James M, Scott, Brian L, Neu, Mary P
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 15-09-2008
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic8009139

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 tBuNH2 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.