Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C5Me4R)2UBr2, (C5Me4R)2U(O-2,6-iPr2C6H3)(Br), and [K(THF)][(C5Me4R)2UBr2] (R = Me, Et)

Inorganics

Alejandro G. Lichtscheidl²  Justin K. Pagano²  Brian L. Scott⁴  Andrew T. Nelson¹  Jaqueline L. Kiplinger²  Stephen Mansell³ 

[1] Materials Science & Technology Division, Los Alamos National Laboratory, Mail Stop E-549, Los Alamos, NM 87545, USA;Chemistry Division, Los Alamos National Laboratory, Mail Stop J-514, Los Alamos, NM 87545, USA;;Chemistry Division, Los Alamos National Laboratory, Mail Stop J-514, Los Alamos, NM 87545, USAMaterials Physics & Applications Division, Los Alamos National Laboratory, Mail Stop J-514, Los Alamos, NM 87545, USA;

关键词: trivalent and tetravalent uranium;    bromide;    organometallic;   

DOI  :  10.3390/inorganics4010001

来源: mdpi

【 摘 要 】

The organometallic uranium species (C₅Me₄R)₂UBr₂ (R = Me, Et) were obtained by treating their chloride analogues (C₅Me₄R)₂UCl₂ (R = Me, Et) with Me₃SiBr. Treatment of (C₅Me₄R)₂UCl₂ and (C₅Me₄R)₂UBr₂ (R = Me, Et) with K(O-2,6-ⁱPr₂C₆H₃) afforded the halide aryloxide mixed-ligand complexes (C₅Me₄R)₂U(O-2,6-ⁱPr₂C₆H₃)(X) (R = Me, Et; X = Cl, Br). Complexes (C₅Me₄R)₂U(O-2,6-ⁱPr₂C₆H₃)(Br) (R = Me, Et) can also be synthesized by treating (C₅Me₄R)₂U(O-2,6-ⁱPr₂C₆H₃)(Cl) (R = Me, Et) with Me₃SiBr, respectively. Reduction of (C₅Me₄R)₂UCl₂ and (C₅Me₄R)₂UBr₂ (R = Me, Et) with KC₈ led to isolation of uranium(III) “ate” species [K(THF)][(C₅Me₅)₂UX₂] (X = Cl, Br) and [K(THF)_0.5][(C₅Me₄Et)₂UX₂] (X = Cl, Br), which can be converted to the neutral complexes (C₅Me₄R)₂U[N(SiMe₃)₂] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.

【 授权许可】

CC BY   
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