About low oxidation states, hydration and covalence properties of f elements

David, F.

doi:10.1524/ract.2008.1470

Cited by 28 publications

(44 citation statements)

References 33 publications

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“…David et al proposed a model [47] in order to predict and quantify thermodynamic properties of actinide aquo ions as many experimental data are missing. For a meaningful comparison, their data [3] were used as reference although some experimental data exist for lanthanides. Figure 3 reports the correlation between the resulting AMOEBA values and the reference data from David (see Table S9 in supporting information for numerical values).…”

Section: Resultsmentioning

confidence: 99%

“…However, due to the high instability of most of the 5f elements, many basic physico-chemical characteristics are still not experimentally accessible. For instance, ionization potentials or thermodynamic properties, such as hydration and binding free energies, have only been estimated by using empirical extrapolation models [3,4]. Nevertheless, these data still remain a reference for these elements.…”

Section: Introductionmentioning

confidence: 99%

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Hydration gibbs free energies of open and closed shell trivalent lanthanide and actinide cations from polarizable molecular dynamics

et al. 2014

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The hydration free energies, structures, and dynamics of open- and closed-shell trivalent lanthanide and actinide metal cations are studied using molecular dynamics simulations (MD) based on a polarizable force field. Parameters for the metal cations are derived from an ab initio bottom-up strategy. MD simulations of six cations solvated in bulk water are subsequently performed with the AMOEBA polarizable force field. The calculated first-and second shell hydration numbers, water residence times, and free energies of hydration are consistent with experimental/theoretical values leading to a predictive modeling of f-elements compounds.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Hydration gibbs free energies of open and closed shell trivalent lanthanide and actinide cations from polarizable molecular dynamics

et al. 2014

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“…Standard M 3+ /M 2+ reduction potentials for the homologous Ln 3+ (red) and An 3+ (blue) ions. 1 The horizontal dotted green line indicates the separation between those lanthanides that exhibit divalent chemistry according to reaction 1 from those that retain the trivalent oxidation state. Figure 1 (version 1).…”

Section: Supporting Informationmentioning

confidence: 99%

“…The dominant oxidation state of all the lanthanides is trivalent Ln III , though tetravalent and divalent states exist under relatively moderate chemical conditions, notably Ce IV , Sm II , Eu II and Yb II . 1 Divalent and tetravalent oxidation states have been attained for several additional lanthanides under more extreme or exotic conditions. Notably, Evans and co-workers have prepared formally Ln II compounds for all of the lanthanides (except synthetic Pm).…”

Section: Introductionmentioning

confidence: 99%

Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(ii)

et al. 2016

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The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf(II) is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf(II)(CH3SO2)3(-), prepared in the gas phase by reductive elimination of CH3SO2 from Cf(III)(CH3SO2)4(-). Comparison with synthesis of the corresponding Sm and Cm complexes reveals reduction of Cf(III) and Sm(III), and no evidence for reduction of Cm(III). This reflects the comparative 3+/2+ reduction potentials: Cf(3+) (-1.60 V) ≈ Sm(3+) (-1.55 V) ≫ Cm(3+) (-3.7 V). Association of O2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. The new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf(II) coordination complexes and similar chemistry of Cf and Sm.

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“…Although nominated for the Nobel Prize he did not receive it but perhaps, as even a higher distinction, the artificial (1955) radioactive element of atomic number 101, Mendelevium Md, carries his name. We note encouragingly how much is known about the energetics of this element and its ions and compounds, the thermochromatographic behavior of its hexafluoroacetylacetonate [115], lattice energies of diverse salts [116] and the covalency dependence with oxidation state [117].…”

Section: Issuementioning

confidence: 97%

Interplay of thermochemistry and Structural Chemistry, the journal (volume 18, 2007) and the discipline

Ponikvar

Liebman

2008

Struct Chem

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In this study, we relate the contents of the journal Structural Chemistry for the calendar year 2007 and thermochemistry. The year's articles were briefly summarized and a thermochemical comment written to supplement them. Frequently questions were asked and future research was suggested.Keywords Structural Chemistry Á Thermochemistry Á Thermodynamics Á Enthalpy of formation Á Enthalpy of phase change Á Enthalpy of reaction As practiced disciplines, structural chemistry and thermochemistry are very often unrelated. In this study, these disciplines are linked as relations are explicitly made using the contents of the journal Structural Chemistry (Vol. 18) for the calendar year 2007 as a scaffold for our analysis, for our selected articles in the discipline of structural chemistry. These studies have been reviewed by us, where we give them a thermochemical flavor. While this commentary is most generally written in terms of brief summaries of literature papers involving enthalpies of formation and/or reaction, not uncommonly we raise questions and even suggest possible future research. We are not, however, going to give a thermochemical slant on book reviews, honorary dedications, and obituaries although these works will be cited in our text.As such, this article is a sequel to our earlier related reviews of Structural Chemistry for the calendar years 2000 through 2004 [1-5]. Reviews for 2005 and 2006 are currently being prepared. Issue 1In the first article in the first issue of Structural Chemistry for 2007, Hargittai [6] asserted that while research is currently usually carried out in big groups, the most important ideas, observations and discoveries still belong to individuals who have to bring down dogmas or open entirely new areas in science. This may bring solace to the thermochemical community in which research groups are generally small, and the number of new practitioners sadly few.In the past decade, the crystal engineering of multidimensional arrays and networks containing metal ions has achieved considerable progress because of the increased interest in the potential utility of these compounds as zeolite-like materials [7-11], catalysts [12], or magnetic materials [13][14][15]. The thermochemistry of these species is complicated by their inherent complexity: however, estimation approaches of their key thermochemical quantities are increasingly reliable [16]. In the second article of this issue, by Wang et al. [17], the versatility of malonate dianion as a ligand for the construction of extended networks with different topologies dependent on the coordination geometry of the metal ion was discussed. The synthesis and structure of a novel malonate-bridged copper(II) compound in which copper(II) ions have two different coordination environments in a novel three-dimensional (3D) network was described. Metal malonates have been studied from a

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About low oxidation states, hydration and covalence properties of f elements

Cited by 28 publications

References 33 publications

Hydration gibbs free energies of open and closed shell trivalent lanthanide and actinide cations from polarizable molecular dynamics

Hydration gibbs free energies of open and closed shell trivalent lanthanide and actinide cations from polarizable molecular dynamics

Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(ii)

Interplay of thermochemistry and Structural Chemistry, the journal (volume 18, 2007) and the discipline

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