Electrochemical Properties of Bis(dicarbollide)uranium Dibromide

Rege, Francis M. de; Smith, W. H.; Scott, Brian L.; Nielsen, Jens Bo; Kd, Abney

doi:10.1021/ic9712838

Cited by 14 publications

(3 citation statements)

References 15 publications

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“…These bond lengths are consistent with other U(III) bromide complexes. [21][22][23] The U-O bond lengths range from U1-O3 = 2.550(7) A ˚to U1-O2 = 2.656(7) A ˚, which is comparable to those reported for other DME complexes of uranium. 24-26…”

Section: Resultssupporting

confidence: 76%

Reactivity of UH3 with mild oxidants

Schnaars

Hayton

2008

Dalton Trans.

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Addition of 2 equiv of I2 to a stirring suspension of UH3 in Et2O results in vigorous gas evolution and the formation of UI4(OEt2)2 (1), which can be isolated in good yields as an air- and moisture-sensitive brick-red powder. Addition of 3 equiv of AgBr to UH3 in DME produces UBr3(DME)2 (2), while addition of 4 equiv of AgX to UH3 in DME-CH2Cl2 provides UX4(DME)2 (X = Br, 3; Cl, 4). Similarly, the reaction of 4 equiv of AgOTf with UH3 in neat DME generates U(OTf)4(DME)2 (5). Each of these reactions proceeds with the evolution of hydrogen. Complex can also be generated by reaction of 4 equiv of Me3SiI with UCl4 in Et2O. All complexes were fully characterized, including analysis by X-ray crystallography.

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Section: Resultssupporting

confidence: 76%

Reactivity of UH3 with mild oxidants

Schnaars

Hayton

2008

Dalton Trans.

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“…For (26), t Bu (27)), respectively [7,[23][24][25]. Complex (C 5 Me 5 ) 3 UBr (22) is thermally unstable and leads to isolation of (C 5 Me 5 ) 2 UBr (28), from which (C 5 Me 5 ) 2 UBr(THF) (29) can be formed [20].…”

Section: Introductionmentioning

confidence: 99%

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)

et al. 2016

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Abstract:The organometallic uranium species (C 5 Me 4 R) 2 UBr 2 (R = Me, Et) were obtained by treating their chloride analogues (C 5 Me 4 R) 2 UCl 2 (R = Me, Et) with Me 3 SiBr. Treatment of (C 5 Me 4 R) 2 UCl 2 and (C 5 Me 4 R) 2 UBr 2 (R = Me, Et) with K(O-2,6-i Pr 2 C 6 H 3 ) afforded the halide aryloxide mixed-ligand complexes (C 5 Me 4 R) 2 U(O-2,6-i Pr 2 C 6 H 3 )(X) (R = Me, Et; X = Cl, Br). Complexes (C 5 Me 4 R) 2 U(O-2,6-i Pr 2 C 6 H 3 )(Br) (R = Me, Et) can also be synthesized by treating (C 5 Me 4 R) 2 U(O-2,6-i Pr 2 C 6 H 3 )(Cl) (R = Me, Et) with Me 3 SiBr, respectively. Reduction of (C 5 Me 4 R) 2 UCl 2 and (C 5 Me 4 R) 2 UBr 2 (R = Me, Et) with KC 8 led to isolation of uranium(III) "ate" species [K(THF)][(C 5 Me 5 ) 2 UX 2 ] (X = Cl, Br) and [K(THF) 0.5 ][(C 5 Me 4 Et) 2 UX 2 ] (X = Cl, Br), which can be converted to the neutral complexes (C 5 Me 4 R) 2 U[N(SiMe 3 ) 2 ] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.

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“…Besides the extensively studied metal–flat homocyclic ligand sandwich clusters, efforts have also been made on cage ligand-like sandwich clusters, such as metal–fullerene sandwich clusters. ,− Dicarbollide (1,2-C 2 B 9 H 11 , abbreviated as Dcb hereafter), one of the most widely studied carboranes, might be another prominent cage ligand and could form sandwich clusters such as iron bis(dicarbollide), an analogue of ferrocene, because Dcb shows similar or even greater electron acceptor property than the Cp ligand. , In fact, the ferrocene-like TM-Dcb (TM(Dcb) 2 , TM = Fe, Co, ,− Ni, ,, Cu − ) sandwich clusters have been successfully synthesized and characterized experimentally. Theoretically, Bühl et al − studied the structures and 11 B NMR chemical shifts of TM(Dcb) 2 (TM = Fe, Co, Ni, Ru, Rh, Pd).…”

Section: Introductionmentioning

confidence: 99%

Structural, Electronic, and Magnetic Properties of Neutral and Charged Transition Metal–Bis(dicarbollide) Sandwich Clusters

et al. 2011

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Structural, electronic, and magnetic properties of transition metal (TM)–bis(dicarbollide) (TM(Dcb)2; TM = Sc–Mn, Dcb = dicarbollide) sandwich clusters and their charged counterparts (TM(Dcb)2 +, TM(Dcb)2 –) are systematically investigated by using all electron density functional theory approach. All TM(Dcb)2 sandwich clusters are highly stable because of the formation of ionic–covalent bonding. The Ti(Dcb)2 is the most stable, the Sc- and V(Dcb)2 are intermediate, and the Cr- and Mn(Dcb)2 are the least stable. The magnetic moment of TM(Dcb)2 exhibits a clear element-dependent variation with 1 μB for Sc(Dcb)2 and 0 μB for Ti(Dcb)2 and with a linear increased trend by 1 μB from Ti(Dcb)2 to Mn(Dcb)2. This element-dependent magnetic behavior can be well understood by electron transfer as well as spin density distribution. We further reveal that charging can induce the rotation of the ligands in the Sc-, V-, Cr-, and Mn(Dcb)2 clusters, which makes them promising candidates for molecular motors.

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Electrochemical Properties of Bis(dicarbollide)uranium Dibromide

Cited by 14 publications

References 15 publications

Reactivity of UH3 with mild oxidants

Reactivity of UH3 with mild oxidants

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)

Structural, Electronic, and Magnetic Properties of Neutral and Charged Transition Metal–Bis(dicarbollide) Sandwich Clusters

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