The chemistry of trivalent uranium: The synthesis and reaction chemistry of the tetrahydrofuran adduct of uranium trichloride, UCl3(THF)x

doi:10.1016/0022-1902(79)80439-X

Journal of Inorganic and Nuclear Chemistry

Volume 41, Issue 4, 1979, Pages 533-535

https://doi.org/10.1016/0022-1902(79)80439-X Get rights and content

Abstract

Uranium tetrachloride in THF solution has been found to react with NaH to yield UCl₃(THF)_x. From this solution the 1:1 adduct UCl₃(THF) has been isolated. Unlike the parent UCl₃, this material is soluble in THF enabling the study of a variety of reactions. The reactions of UCl₃(THF)_x with 4-picoline-N-oxide, TICp, NaCp and NaBH₄ have been studied as well as the decomposition of UCl₃(THF) at elevated temperatures.

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This review presents the preparation procedures and characterisations of almost all hitherto identified tervalent uranium compounds. Emphasis is placed on crystallographic and optical properties of the compounds. Spectroscopic properties of uranium(3+) doped single crystals are also discussed. Extensive physical data of the compounds, such as crystallographic, thermodynamic, infrared and magnetic data as well as atomic and crystal-field parameters are summarized in a table.
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2004, Comprehensive Coordination Chemistry II
Derivative chemistry of [UCl<inf>2</inf>{B(pz)<inf>4</inf>}<inf>2</inf>]: Stability of complexes containing the fragments [U{B(pz)<inf>4</inf>}<inf>2</inf>] and [U{HB(pz)<inf>3</inf>}<inf>2</inf>]
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Uranium tetrachloride reacts with two equivalents of K[B(pz)₄] in THF affording [UCl₂{B(pz)₄}₂] (1) in 75% yield. Complex 1 is monomeric and crystallizes in the monoclinic space group C2/c with cell parameters a=13.700(6), b=12.759(2), c=17.513(8) Å, β=101.37(2)°, V=3001(2) Å³, Z=4. Derivatives [UCl(OR){B(pz)₄}₂] (R=C₂H₅ (2), ^tBu (3), C₆H₄-o-OMe (4) and C₆H₂-2,4,6-Me₃ (5)), [U(O^tBu)₂{B(pz)₄}₂] (6), [U(SⁱPr)₂{B(pz)₄}₂] (7) and [UCl(Me){B(pz)₄}₂] (8) were obtained by reacting 1 with sodium alkoxides, with NaSⁱPr or with LiMe. X-ray crystallographic analysis of 5 and 7 shows that uranium is eight-coordinate by the two η³-[B(pz)₄] ligands and by two monodentate coligands (5: crystallizes in the monoclinic space group C2/c with cell parameters a=30.575(3), b=9.929(1), c=24.884(3) Å, β=90.59(1)°, V=7554(1) Å³, Z=8; 7 crystallizes in the monoclinic space group C2/c with cell parameters a=24.286(7), b=9.471(2), c=16.076(3) Å, β=96.44(3)°, V=3674(2) Å³, Z=4). Extended Hückel molecular orbital (EHMO) calculations were used to get a better insight into the electronic properties of the ligand [B(pz)₄] and to get some explanation on the relative stability of complexes containing the fragments ‘[U{B(pz)₄}₂]’ and ‘[U{HB(pz)₃}₂]’.
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1998, Inorganica Chimica Acta
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^☆: Work supported by the U.S. Department of Energy.

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Journal of Inorganic and Nuclear Chemistry

Abstract

References (14)

J. Organometal. Chem.

Acta. Cryst.

J. Chem. Phys.

J. Chem. Soc. (Dalton Trans.)

Inorg. Chem.

Compt. Rend. (C)

Inorg. Syn.

Cited by (58)

Electrochemical and spectroscopic investigations of uranium(III) with N,N,N′,N′-tetramethylmalonamide in DMF

Expanding the chemistry of U<sup>3+</sup> reducing agents

Tervalent uranium compounds

The Actinides

Derivative chemistry of [UCl<inf>2</inf>{B(pz)<inf>4</inf>}<inf>2</inf>]: Stability of complexes containing the fragments [U{B(pz)<inf>4</inf>}<inf>2</inf>] and [U{HB(pz)<inf>3</inf>}<inf>2</inf>]

Chloride ion transfer during the U(IV)/I(III) reduction of UCl<inf>4</inf> in tetrahydrofuran (THF), studied by cyclic voltammetry; synthesis and molecular structure of [NBu<inf>4</inf>][UCl<inf>5</inf>(THF)]

The chemistry of trivalent uranium: The synthesis and reaction chemistry of the tetrahydrofuran adduct of uranium trichloride, UCl3(THF)x☆

Abstract

J. Organometal. Chem.

Acta. Cryst.

J. Chem. Phys.

J. Chem. Soc. (Dalton Trans.)

Inorg. Chem.

Compt. Rend. (C)

Inorg. Syn.

The chemistry of trivalent uranium: The synthesis and reaction chemistry of the tetrahydrofuran adduct of uranium trichloride, UCl₃(THF)_x☆