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Inorganics 2016, 4(1), 1; doi:10.3390/inorganics4010001

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)

1
Chemistry Division, Los Alamos National Laboratory, Mail Stop J-514, Los Alamos, NM 87545, USA
2
Materials Physics & Applications Division, Los Alamos National Laboratory, Mail Stop J-514, Los Alamos, NM 87545, USA
3
Materials Science & Technology Division, Los Alamos National Laboratory, Mail Stop E-549, Los Alamos, NM 87545, USA
*
Authors to whom correspondence should be addressed.
Academic Editors: Stephen Mansell and Steve Liddle
Received: 23 November 2015 / Revised: 9 December 2015 / Accepted: 11 December 2015 / Published: 6 January 2016
(This article belongs to the Special Issue Rare Earth and Actinide Complexes)
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Abstract

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. View Full-Text
Keywords: trivalent and tetravalent uranium; bromide; organometallic trivalent and tetravalent uranium; bromide; organometallic
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MDPI and ACS Style

Lichtscheidl, A.G.; Pagano, J.K.; Scott, B.L.; Nelson, A.T.; Kiplinger, J.L. 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 2016, 4, 1.

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