Electrochemical study of uranium(IV) and uranium(IV) organometallic compounds in tetrahydrofuran by means of conventional microelectrodes and ultramicroelectrodes

Hauchard, Didier; Cassir, Michel; Chivot, J.; Ephritikhine, Michel

doi:10.1016/0022-0728(91)85182-o

Cited by 29 publications

(13 citation statements)

References 17 publications

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“…An ECE mechanism corresponds to an electron transfer (ET) process initially and then finally with a chemical reaction in the middle of the two ET processes. However, we did not observe any evidence such as current for the reduction of uranium(VI) [25].…”

Section: Electrochemical Propertiescontrasting

confidence: 86%

Study of the histidine complex of uranium(IV): synthesis, spectrophotometric, magnetic and electrochemical properties

Nazir¹,

Khattak²,

Khan³

et al. 2021

Bull. Chem. Soc. Eth.

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We synthesized the novel histidine complex of uranium(IV). A 1:3 mole ratio was found between metal and ligand by the mole ratio method, while –NH2 and –COO– groups of histidine behave as coordinating sites. The IR spectra confirmed the lone pair donating or coordinating sites. The elemental analysis confirmed the stoichiometry. The bathochromic shift with an increase in the optical density in the UV-Visible range indicated that the compound and its central metal ion hold uniform electronic charge distribution. The electrochemical results indicated a quasi-reversible (neither completely reversible nor completely irreversible) oxidation of the complex to its uranium(V) product at the platinum working electrode. The quasi-reversible process shows a comparatively slow electron transfer (ET) rate with the heterogeneous electron transfer rate constant ‘ks’ (3.4 × 10–4 cm s-1) at 50 mV s-1 and 305 ± 0.5 K. The kinetics such as diffusion and charge transfer lead the reaction with an ECE (electrochemical–chemical–electrochemical) mechanism. The thermodynamic parameters of activation such as ΔH*; 4.257 kJ mol–1, ΔS*; -2.519 × 10–3 J mol–1 K–1 and ΔG* 4.26 kJ mol–1 helped to propose an associative mechanism of the electron transfer at the platinum working electrode. KEY WORDS: Uranium, Histidine, Spectroscopy, Electrochemistry, Kinetics Bull. Chem. Soc. Ethiop. 2020, 34(3), 557-569. DOI: https://dx.doi.org/10.4314/bcse.v34i3.11

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Section: Electrochemical Propertiescontrasting

confidence: 86%

Study of the histidine complex of uranium(IV): synthesis, spectrophotometric, magnetic and electrochemical properties

Nazir¹,

Khattak²,

Khan³

et al. 2021

Bull. Chem. Soc. Eth.

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“…N s-interaction. [46] This provides a clear illustration of how both the nature and extent of covalency may be evaluated experimentally when a pair of isostructural molecules with varying energetics is available. However, this type of analysis has only limited value in other systems, as relatively few such pairs exist, and making comparisons regarding electronic structure between systems that are not strictly isostructural can be difficult.…”

Section: Energetic Criteria For Covalent/ionic Bondingmentioning

confidence: 98%

Evaluating f‐Element Bonding from Structure and Thermodynamics

Minasian

Krinsky

Arnold

2011

Chemistry A European J

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The practical goal to measure and understand the thermodynamic properties of molecules and materials containing f-elements is often achieved through indirect methods. Of the characterization tools available to inorganic chemists, few are more powerful than X-ray crystallography. Yet for lanthanides and actinides, interpretation of a bond length is a challenging undertaking that involves a complex interplay of steric and electronic forces. In this Concept article, we perform an analysis of selected examples in which structural criteria alone have been used to draw qualitative conclusions about chemical bonding. In other instances for which such an analysis is not valid, thermodynamic information is evaluated side by side with structural data to provide reasonable interpretations of a covalent/ionic mode of bonding. A geometric variation larger than 3σ is not necessarily correlated to a change in bonding, nor is an increase in bond energy related to a bond with more covalent character. However, careful consideration of thermodynamic information can lead to reasonable interpretations of electronic structure, and may provide a more reliable benchmark for the theoretical methods which can describe f-elements.

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“…The U(V) species formed by the oxidation of U(IV) is unstable and disproportionates into U(IV) and U(VI). No reduction current due to U(VI) species was observed [15].…”

Section: Electrochemical Studiesmentioning

confidence: 94%

Synthesis, Spectral and Electrochemical Studies of Complex of Uranium(IV) with Pyridine-3-Carboxylic Acid

Nazir¹,

Naqvi²

2013

AJAC

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The investigation of complexation of uranium with biological active ligands is vital for understanding uranium speciation in biosystems. A number of studies have been undertaken for investigating the complexation of uranium in its (VI) oxidation states but similar investigations pertaining to the interaction of uranium, in lower oxidation states, with biological ligands is scarce. The aim of the work is to bridge this gap and studies have been carried out to determine the coordination pattern of pyridine-3-carboxylic acid with uranium(IV). Semi-micro analysis, spectro-analytical techniques, magnetic susceptibility and cyclic voltammetry have been employed for the characterization of the synthesized complex.

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Electrochemical study of uranium(IV) and uranium(IV) organometallic compounds in tetrahydrofuran by means of conventional microelectrodes and ultramicroelectrodes

Cited by 29 publications

References 17 publications

Study of the histidine complex of uranium(IV): synthesis, spectrophotometric, magnetic and electrochemical properties

Study of the histidine complex of uranium(IV): synthesis, spectrophotometric, magnetic and electrochemical properties

Evaluating f‐Element Bonding from Structure and Thermodynamics

Synthesis, Spectral and Electrochemical Studies of Complex of Uranium(IV) with Pyridine-3-Carboxylic Acid

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