The Crystal Structure of [(UO2)4Cl2O2(OH)2(H2O)6].4H2O, a Compound Containing a Tetranuclear Aquachlorohydroxooxo Complex of Uranyl(VI).

Åberg, Märtha; Cabrini, A.; Scibona, G.; Johansson, G.; Sandström, M.

doi:10.3891/acta.chem.scand.30a-0507

Cited by 28 publications

(17 citation statements)

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“…Compounds containing this cluster appear to form exclusively as precipitates; it has not been proposed as a solution form of uranyl, and in at least one report, it is undetectable in the mother solution from which it crystallized . The crystallization of these compounds is similar to what we observed: An initially acidic uranyl chloride solution is treated with a base, separated from a precipitate, and allowed to stand until crystals form. , Given that crystals of 1,4-(DAO)Bz form alongside this compound, it is likely that the solution (after precipitation) contains discrete, soluble uranyl amidoximate complexes, but with time, some of the anionic 1,4-(DAO)Bz ligands are protonated and exchanged with hydroxide or oxo ligands in hydrolysis reactions to form the far less soluble UMOFUA which precipitates immediately.…”

supporting

confidence: 76%

A Uranyl Metal Organic Framework Arising from the Coordination of a Partially Hydrolyzed Tetrauranyl Node with the Tautomerically Diverse 1,4-(Diamidoximyl)benzene Ligand

Mishra

Patil

Kelley

et al. 2019

Crystal Growth & Design

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We report a unique uranium-based metal organic framework afforded from the spontaneous reaction of 1,4-(diamidoximyl)benzene (1,4-(DAO)Bz) with uranyl chloride. The structure is the first reported example to show either hydrolysis alongside amidoxime coordination or the presence of multiple amidoxime protonation states in a single complex. The ability of the ligand to adopt three chemically distinct forms affords it enough flexibility to link the typically planar uranyl nodes in three orthogonal directions, giving rise to a cationic framework with large channels and suggesting applications for this system in crystal engineering.

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supporting

confidence: 76%

A Uranyl Metal Organic Framework Arising from the Coordination of a Partially Hydrolyzed Tetrauranyl Node with the Tautomerically Diverse 1,4-(Diamidoximyl)benzene Ligand

Mishra

Patil

Kelley

et al. 2019

Crystal Growth & Design

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“…The structures are similar to [(U0 2 ) 3 0(0H) 3 (H 2 0) 6 ]N0 3 · 4H 2 0 [13]. We have assumed that the complex (5,-8) contains an extension of the bridging system found in the solid state structures of [(U0 2 ) 4 C1 2 0 2 (0H) 2 (H 2 0) 6 ] · 4H 2 0 [14], and [(U0 2 ) 4 C1 4 0 2 (0H) 2 (C 4 H 8 0) 2 -(H 2 0) 4 ] [15], i.e. three bridging oxide ions.…”

Section: (S0 4 ) R Complexesmentioning

confidence: 97%

Ternary Metal Complexes. 2. The U(VI) – SO^2- ₄ – OH^- System

Grenthe

Lagerman

1993

Radiochimica Acta

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The complexes formed in the ternary system U(VI) -S0 4~ -OH" have been investigated at 25.00 °C using Potentiometrie titrations in a 0.500 M Na 2 S0 4 + 2.00 M NaC10 4 ionic medium. The conditional equilibrium constants log*Xp,(log*.K 2 _ 2 = -8.39 ± 0.08, log*tf 3 _ 4 = -16.64 ± 0.09, and log*A: 5 -8 = -32.98 + 0.10), for the reactions/>U0| + +?H 2 0 + rS0 4~ "(υ0 2 ) ρ (0Η)," + gH + , have been determined from these data."(U0 2 ) p (0H)," denotes all the ternary complexes with the same stoichiometric coefficients p,q, andA previous experimental study by Peterson (Acta Chem. Scand. 15, 101 (1961)) has been reinterpreted. This showed that the model proposed by Peterson is not the best one, the model presented in the present study gives a much better agreement with the experimental data. The equilibrium constants in our reinterpretation are log*Ä^2-2 = -8.23 + 0.06, log*AT 3 _ 4 = -16.06 ± 0.06, and log ».Ks-β = -32.03 ± 0.06. The magnitude of the equilibrium constant for the (2, -2) species is very different from the value found in Perchlorate media (\og*ß 2 -2 = -5.74 + 0.07), furthermore complexes with (p,q) equal to (3,-4) and (5,-8) are not formed there. These facts indicate that ternary sulphate containing species are formed in sulphate media. From the magnitude of the equilibrium constants and the known structures and coordination geometries of uranium(VI) complexes we propose the following stoichiometry of the ternary complexes: (U0 2 ) 2 (0H) 2 (S0 4 ) 2 ~, (U0 2 ) 3 (0)(S0 4 ) 3 (0H)r (or (U0 2 ) 3 (0)(S0 4 ) 4 (0H)D and (U0 2 ) 5 (0) 3 (S0 4 ) 5 (0H)i°-. The experimental finding indicate that the main features of the oxide/hydroxide bridges are retained in the ternary complexes, and that sulphate can be bonded both in a bridging and a terminal fashion. The bonding of sulphate is sufficiently strong to influence the speciation of uranium in some ground and surface water systems.

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“…been observed for the shortest U-O bridge bond in similar tetranuclear uranyl complexes (Aberg, 1976;Perrin & Le Marouille, 1977).…”

mentioning

confidence: 71%

Structure of trans-dibromotetrakis(pyridine)rhodium(III) bromide hexahydrate

Muir¹,

Gomez²,

Muir³

et al. 1987

Acta Crystallogr C

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The Crystal Structure of [(UO2)4Cl2O2(OH)2(H2O)6].4H2O, a Compound Containing a Tetranuclear Aquachlorohydroxooxo Complex of Uranyl(VI).

Cited by 28 publications

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A Uranyl Metal Organic Framework Arising from the Coordination of a Partially Hydrolyzed Tetrauranyl Node with the Tautomerically Diverse 1,4-(Diamidoximyl)benzene Ligand

A Uranyl Metal Organic Framework Arising from the Coordination of a Partially Hydrolyzed Tetrauranyl Node with the Tautomerically Diverse 1,4-(Diamidoximyl)benzene Ligand

Ternary Metal Complexes. 2. The U(VI) – SO^2- ₄ – OH^- System

Structure of trans-dibromotetrakis(pyridine)rhodium(III) bromide hexahydrate

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The Crystal Structure of [(UO2)4Cl2O2(OH)2(H2O)6].4H2O, a Compound Containing a Tetranuclear Aquachlorohydroxooxo Complex of Uranyl(VI).

Cited by 28 publications

References 0 publications

A Uranyl Metal Organic Framework Arising from the Coordination of a Partially Hydrolyzed Tetrauranyl Node with the Tautomerically Diverse 1,4-(Diamidoximyl)benzene Ligand

A Uranyl Metal Organic Framework Arising from the Coordination of a Partially Hydrolyzed Tetrauranyl Node with the Tautomerically Diverse 1,4-(Diamidoximyl)benzene Ligand

Ternary Metal Complexes. 2. The U(VI) – SO2- 4 – OH- System

Structure of trans-dibromotetrakis(pyridine)rhodium(III) bromide hexahydrate

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Ternary Metal Complexes. 2. The U(VI) – SO^2- ₄ – OH^- System