Dimethylsuphoxide and its roles in the coordination chemistry of the uranyl ion

Harrowfield, Jack M.; Skelton, Brian W.; White, Allan H.

doi:10.1016/j.crci.2004.10.009

Cited by 24 publications

(3 citation statements)

References 54 publications

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“…However, the maximum displacement of 0.244 Å is much less than the value of 0.42 Å, which was considered as the upper limit for cyclopentadienyl complexes with conventional M−C(C 5 R 5 ) bond distances and angles and no unusual ring reactivity . The complexes adopt a pentagonal bipyramidal configuration, with the Cp* ligands, considered as monodentate, in apical positions and the five acetonitrile molecules in the equatorial plane; this geometry is reminiscent of that of the uranyl(VI) complexes [UO 2 (L) 5 ] 2+ . The mean U−C distance in 6 − 8 is 0.05−0.1 Å larger than in the bent metallocenes 3 − 5 , as expected from the increase of the coordination number by two units, whereas the average lengthening of the U−N distance is only 0.02 Å, likely reflecting the higher Lewis acidic character of the metal center in the dicationic complex.…”

Section: Resultsmentioning

confidence: 99%

From Bent to Linear Uranium Metallocenes: Influence of Counterion, Solvent, and Metal Ion Oxidation State

et al. 2006

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Reactions of Cp*2UCl2 with a slight excess of Me3SiI or Me3SiOTf in acetonitrile provide convenient routes to Cp*2UI2 (1) or Cp*2U(OTf)2 (2) (Cp* = η-C5Me5; OTf = OSO2CF3), which were isolated with excellent yields. Crystals of the bent metallocenes Cp*2UI2(NCR) (R = Me (3), tBu (4)) have been obtained by addition of excess RCN to a toluene solution of 1. The triflate analogue Cp*2U(OTf)2(NCMe) (5) contains monodentate OTf ligands. Treatment of Cp*2UMe2 with 2 equiv of HNEt3BPh4 in acetonitrile led to the immediate formation of [Cp*2U(NCMe)5][BPh4]2 (6). The 1H NMR spectra of 1 and 2 in acetonitrile are similar to that of 6, indicating the presence of the dicationic species [Cp*2U(NCMe)5][X]2 [X = I (7), OTf (8)] in this solvent. Compounds 6−8 are the first linear metallocenes of an f-element and exhibit an unprecedented structure with auxiliary donor ligands in the equatorial plane parallel to the cyclopentadienyl rings. When treated with Me3SiOTf, the uranium(III) species Cp*2UCl2Na(thf)2 did not afford the trivalent complex Cp*2U(OTf) (9) but gave crystals of the dimeric uranium(IV) “ate” compound [Cp*2U(OTf)3Na(thf)2]2·2(CH2)4O (10·2(CH2)4O). The first organouranium(III) triflate, 9, was isolated in 90% yield from the reaction of U(OTf)3 with 2 equiv of KCp* in thf. Dissolution of Cp*2UI(py) in acetonitrile gave the adduct Cp*2UI(NCMe)2 (11), which, like its cerium analogue, adopts a bent sandwich structure in its crystalline form. The 1H NMR spectra of 11 and Cp*2U(OTf)(NCMe)2 are similar in benzene and acetonitrile, suggesting that the trivalent linear metallocene [Cp*2U(NCMe)5][X] (X = I or OTf) is not present in pure acetonitrile. These observations are confirmed by the addition of 3 equiv or excess MeCN to a solution of [Cp*2U(thf)2][BPh4] in thf, which afforded the stable [Cp*2U(NCMe)3][BPh4] as the sole product.

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Section: Resultsmentioning

confidence: 99%

From Bent to Linear Uranium Metallocenes: Influence of Counterion, Solvent, and Metal Ion Oxidation State

et al. 2006

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“…The presence of coordinated DMSO molecule(s) in the complex in solution is further corroborated by the appearance of a singlet signal at δ 2.62 ppm, slightly downfield shifted from the main -CH 3 signal of the non-deuterated percentage of the solvent (at δ 2.50 ppm). It is well established that the dipolar, aprotic solvent DMSO is a strong O-bonded donor to the uranyl ion [58].…”

Section: Spectroscopic Characterization Of 1 In Briefmentioning

confidence: 99%

Two different coordination modes of the Schiff base derived from ortho-vanillin and 2-(2-aminomethyl)pyridine in a mononuclear uranyl complex

Tsantis

Lada

Tzimopoulos

et al. 2022

Heliyon

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“…Lead(II) picrate [4] provides an example of this situation, our numerous efforts to obtain crystals suitable for diffraction measurements from aqueous solution failing until, using a strategy found to be useful in the face of similar difficulties encountered with uranyl picrate [5], the material was converted to its dimethylsulfoxide (dmso) solvate. Attempts to obtain mercury(II) picrate led to confrontation with different problems.…”

Section: Introductionmentioning

confidence: 99%

Lattice Forces in Heavy Metal Picrates: Structural Characterization of Lead and Mercury Species

Arnaud‐Neu¹,

Harrowfield

Michel³

et al. 2005

Supramolecular Chemistry

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Structure determinations for the dimethylsulfoxide (dmso) solvate of lead(II) picrate (picrate 5 pic 5 2,4,6-trinitrophenoxide), formally a centrosymmetric dimer, [Pb 2 (dmso) 4 (pic) 4 ], and for unsolvated mercury(I) picrate, a polymer of conventional mercurous dimers, [Hg 2 (-pic) 2 ] n , show that, despite considerable differences in the form of the metal unit, there are remarkable similarities in the mode of coordination of the bridging picrate ligands. In both lattices, parallel arrays of picrate rings can be discerned but appear to be associated with short N· · ·O, O· · ·O or O· · ·C contacts rather than C· · ·C. In the Pb compound, there is also evidence of intramolecular contacts to dmso-S.

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Dimethylsuphoxide and its roles in the coordination chemistry of the uranyl ion

Cited by 24 publications

References 54 publications

From Bent to Linear Uranium Metallocenes: Influence of Counterion, Solvent, and Metal Ion Oxidation State

From Bent to Linear Uranium Metallocenes: Influence of Counterion, Solvent, and Metal Ion Oxidation State

Two different coordination modes of the Schiff base derived from ortho-vanillin and 2-(2-aminomethyl)pyridine in a mononuclear uranyl complex

Lattice Forces in Heavy Metal Picrates: Structural Characterization of Lead and Mercury Species

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