Formation constants for complexes of transition-metal cations with O- and N-donor ligands in aqueous solutions

Mishustin, A. I.

doi:10.1134/s003602360702026x

Cited by 8 publications

(8 citation statements)

References 24 publications

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“…Priorreported X-ray absorption spectra for TM II -sulfates,aswell as calculated and empirical stability constants,s hows that Zns full 3d 10 shell, minimizes covalent contributions to bonding with sulfate,meaning sulfate-zinc bonding is less favorable. [23] As aforementioned, we believe the higher TM II concentration slows assembly of Ce 70 rings,retaining more Ce-monomers as Ce 70 framework-linkers.T herefore,t he isolated-framework topology was also obtained with higher concentration Co II . [a] Aspect ratio = (cylinderheight/cylinder diameter).…”

Section: Ce 70 -Isolated Frameworkmentioning

confidence: 59%

Ce^IV₇₀Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

Colliard

Nyman

2021

Angewandte Chemie

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MIV molecular oxo‐clusters (M=Zr, Hf, Ce, Th, U, Np, Pu) are prolific in bottoms‐up material design, catalysis, and elucidating reaction pathways in nature and in synthesis. Here we introduce Ce70, a wheel‐shaped oxo‐cluster, [CeIV70(OH)36(O)64(SO4)60(H2O)10]4−. Ce70 crystallizes into intricate high pore volume frameworks with divalent transition metals and Ce‐monomer linkers. Eight crystal‐structures feature four framework types in which the Ce70‐rings are linked as propellers, in offset‐stacks, in a tartan pattern, and as isolated rings. Small‐angle X‐ray scattering of Ce70 dissolved in butylamine, with and without added cations (CeIV, alkaline earths, MnII), shows the metals‘ differentiating roles in ring linking, leading to supramolecular assemblies. The large acidic pores and abundant terminal sulfates provide ion‐exchange behavior, demonstrated with UIV and NdIII. Frameworks featuring CeIII/IV‐monomer linkers demonstrate both oxidation and reduction. This study opens the door to mixed‐metal, highly porous framework catalysts, and new clusters for metal‐organic framework design

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Section: Ce 70 -Isolated Frameworkmentioning

confidence: 59%

Ce^IV₇₀Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

Colliard

Nyman

2021

Angewandte Chemie

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“…We attributed this prior to the competing TM-butylamine ligation-Mn II has lesser tendency to bind the butylamine than the other transition metals. 67 Here we show via SAXS studies that Ce70 exhibits different stacking arrangements than U70 in organic solvents, and the TM II counterions play a more significant role. As identified in the solid state, there are four main architectural building blocks for the TMCe70 frameworks; the Ce70, the TM II and Ce IV monomers, and the ring-bridging sulfates.…”

Section: Supramolecular Assembly In Organic Mediamentioning

confidence: 69%

Supramolecular Assembly of CeIV-Oxo Sulfate Torus with Transition Metal Countercations

Colliard¹,

Nyman²

2020

Preprint

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MIV molecular oxo-clusters of the f- and d-block (M=Zr, Hf, Ce, Th, U, Np, Pu) have been prolific in bottoms-up material design, catalysis, as well as understanding metal oxide assembly, dissolution and surface reactivity in nature and in synthesis. Here we introduce Ce70, a new CeIV wheel-shaped oxo-cluster, [CeIV(OH)36(O)64(SO4)60(H2O)10]4-, isostructural with prior-reported U70. Like U70, Ce70 crystallizes into intricate frameworks with divalent transition metal counter-cations (TMII), and also CeIV-monomer and sulfate addenda ions.

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“…To verify this supposition, in this work we calculated stability constants for sulfate complexes of these metals. The geometric parameter of the Lennard Jones potential σ and the covalence parameter β determined earlier from the values for monohydrates were taken from [15]. The results of calculating the logarithmic ther modynamic stability constants are listed in Table 2, [19] where they are compared with the reported experi mental data (all literature constants given in the table are referred to infinitely dilute solutions).…”

Section: Mishustinmentioning

confidence: 99%

Stability constants of tervalent actinide and lanthanide sulfate complexes in aqueous solutions

Mishustin

2012

Russ. J. Inorg. Chem.

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The determination of thermodynamic and struc tural characteristics of metal complexes in solutions is one of the most important problems of chemistry. Sul fate anions are incorporated into atmospheric aero sols, natural waters, and many minerals and ores. Metal sulfate complexes play an important part in nat ural and engineering processes. Despite the fact that the kinetics and equilibrium of formation of metal sul fate complexes have been studied for many years by different experimental and kinetic methods, their thermodynamic properties (stability constants, etc.) are known only for a restricted number of metals [1]. Owing to experimental difficulties in the operation with radioactive compounds, data for actinides are very scanty. There is no common view on the type of complex formed (inner sphere or outer sphere) in the literature. According to [2], the formation of cation complexes in a solution is considered as a multistage process: first, ions approach each other and form sol vent separated ion pairs (SSIP), some of which may form a contact ion pair (CIP) upon the removal of the water molecule that separates the cation and anion. Studies of sulfate complexes with the use of different techniques (conductometric, potentiometric, and spectroscopic methods, dielectric relaxation spectros copy, ultrasonic dispersion, etc.) bring the authors to contradictory conclusions on the dominant type of complex [3][4][5]. The coordination mode of an anion to a cation in solution (monodentate or bidentate) is also little studied. Different methods were noted to reveal a mixture of inner sphere and outer sphere complexes in aqueous lanthanide and actinide sulfate solutions [3], but there exist disagreements on the dominant type. On the basis of dielectric relaxation measure ments and other literature data, Wachter et al. [4] sup pose that only SSIPs are formed in lithium sulfate solutions, and CIPs are not formed at all even at a con centration of 2 mol/L. A critical view on the possibili ties of spectroscopic methods in the measurements of stability constants of complexes is given in [5] with the use of different metal sulfate complexes as an example.The clarification of a reason for a sharp discrep ancy between the stability constants of 1 : 1 carbonate and sulfate complexes of tervalent lanthanides and actinides in aqueous solutions (the stability constants of carbonate complexes are three to four orders of magnitude higher than those of sulfate complexes) remains to be one of the most intriguing unsolved problems. and anions have close values of crystal ionic radii. Both anions are classified as "hard" according to Pearson's terminology, and tervalent lan thanide and actinide cations are also "hard", so inte rionic interactions are dominantly electrostatic. Close values of the radii of anions with the same charge must have led to close values of stability constants of their complexes (for example, from the viewpoint of Bjer rum's ion association theory, association constants must not differ by more than 10%). An "abnorma...

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Formation constants for complexes of transition-metal cations with O- and N-donor ligands in aqueous solutions

Cited by 8 publications

References 24 publications

Ce^IV₇₀Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

Ce^IV₇₀Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

Supramolecular Assembly of CeIV-Oxo Sulfate Torus with Transition Metal Countercations

Stability constants of tervalent actinide and lanthanide sulfate complexes in aqueous solutions

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Formation constants for complexes of transition-metal cations with O- and N-donor ligands in aqueous solutions

Cited by 8 publications

References 24 publications

CeIV70Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

CeIV70Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

Supramolecular Assembly of CeIV-Oxo Sulfate Torus with Transition Metal Countercations

Stability constants of tervalent actinide and lanthanide sulfate complexes in aqueous solutions

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Product

Resources

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Ce^IV₇₀Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

Ce^IV₇₀Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**