Lanthanide thermodynamic predictions

Bratsch, Steven G.; Silber, Herbert B.

doi:10.1016/s0277-5387(00)87155-7

Cited by 16 publications

(19 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…So, DyF 2 is not considered as thermodynamically stable; this result is in agreement with those obtained by Bratsch et al [19]. According to this diagram, DyF 3 should be electrochemically reduced into Dy, so the only predicted reaction is:…”

Section: Dyf 3 Electrochemical Reduction Mechanism On Inert Electrodesupporting

confidence: 89%

Electrochemical behaviour of dysprosium(III) in LiF–CaF2 on Mo, Ni and Cu electrodes

Saïla¹,

Gibilaro²,

Massot³

et al. 2010

Journal of Electroanalytical Chemistry

View full text Add to dashboard Cite

Section: Dyf 3 Electrochemical Reduction Mechanism On Inert Electrodesupporting

confidence: 89%

Electrochemical behaviour of dysprosium(III) in LiF–CaF2 on Mo, Ni and Cu electrodes

Saïla¹,

Gibilaro²,

Massot³

et al. 2010

Journal of Electroanalytical Chemistry

View full text Add to dashboard Cite

“…Stability of the dihalides are governed in a similar way with decomposition via disproportionation, which is exothermic unless the ratio of the enthalpies of formation for LnX 3 versus LnX 2 is small (<1.5) [32, 40b] . The disproportionation pathway is more likely to be endothermic and therefore stabilize the Ln II state when I 3 is high (Figure 5), which is most likely for Eu, Sm and Yb [40b] . Based on this criterion the halide most likely to stabilize many Ln II ions (Ln = Pr, Nd, Pm, Sm, Eu, Dy, Ho, Er, Tm, Yb) is the iodide ion, which will reduce the lattice energy of both tri‐ and divalent species and so the difference between these will become less significant, favoring the divalent ion, which is indeed reflected in the reported solid state structures [40c, 42] .…”

Section: Fundamentalsmentioning

confidence: 99%

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Hay

Boskovic

2021

Chemistry A European J

View full text Add to dashboard Cite

The development of molecular materials with novel functionality offers promise for technological innovation. Switchable molecules that incorporate redox‐active components are enticing candidate compounds due to their potential for electronic manipulation. Lanthanoid metals are most prevalent in their trivalent state and usually redox‐activity in lanthanoid complexes is restricted to the ligand. The unique electronic and physical properties of lanthanoid ions have been exploited for various applications, including in magnetic and luminescent materials as well as in catalysis. Lanthanoid complexes are also promising for applications reliant on switchability, where the physical properties can be modulated by varying the oxidation state of a coordinated ligand. Lanthanoid‐based redox activity is also possible, encompassing both divalent and tetravalent metal oxidation states. Thus, utilization of redox‐active lanthanoid metals offers an attractive opportunity to further expand the capabilities of molecular materials. This review surveys both ligand and lanthanoid centered redox‐activity in pre‐existing molecular systems, including tuning of lanthanoid magnetic and photophysical properties by modulating the redox states of coordinated ligands. Ultimately the combination of redox‐activity at both ligands and metal centers in the same molecule can afford novel electronic structures and physical properties, including multiconfigurational electronic states and valence tautomerism. Further targeted exploration of these features is clearly warranted, both to enhance understanding of the underlying fundamental chemistry, and for the generation of a potentially important new class of molecular material.

show abstract

“…Although the oxidation state IV is common for Ce, 36 the rather high reduction potential for Ce(IV)/Ce(III) (1.72 V) 34 Alternatively, comparisons can be made by considering the Ln 2+ Ln 3+ ionization energies (IE3), which generally correlate with the Ln 3+ /Ln 2+ reduction potentials. 37,38 Although usually a higher IE3 predicts a higher Ln 3+ /Ln 2+ reduction potential, there are deviations from this correlation. In particular, IE3[Yb] is ca.…”

Section: Reactions With Background Omentioning

confidence: 99%

Electrospray production and collisional dissociation of lanthanide/methylsulfonyl anion complexes: Sulfur dioxide anion as a ligand

Gong

Michelini

Gibson

2015

International Journal of Mass Spectrometry

View full text Add to dashboard Cite

Gas-phase lanthanide-SO 2 complexes, Ln(CH 3 SO 2) 3 (SO 2)-, were produced by collision induced dissociation (CID) of Ln(CH 3 SO 2) 4 precursors prepared by electrospray ionization. For all lanthanides except Eu, CID of Ln(CH 3 SO 2) 4 resulted in CH 3 loss to form Ln(CH 3 SO 2) 3 (SO 2)-, which spontaneously react with O 2 to form Ln(CH 3 SO 2) 3 (O 2)-. CID of Eu(CH 3 SO 2) 4 produced only Eu(CH 3 SO 2) 3-, with reduction from Eu(III) to Eu(II). For Ln = Yb and Sm, the Ln(CH 3 SO 2) 4 underwent neutral ligand loss to form Ln(CH 3 SO 2) 3-, which reacted with O 2 to yield Ln(CH 3 SO 2) 3 (O 2)-, recovering the Ln(III) oxidation state. The CID results parallel condensed phase Ln 3+ /Ln 2+ redox chemistry. Density functional theory (DFT) calculations on Ln(CH 3 SO 2) 3 (SO 2)for Ln = La, Yb and Lu reveal that SO 2 acts as a bidentate oxygen bound ligand for doublet ground state La(CH 3 SO 2) 3 (SO 2)and Lu(CH 3 SO 2) 3 (SO 2)-, while the ground state for Yb(CH 3 SO 2) 3 (SO 2)is an open-shell singlet with a monodentate SO 2 ligand. Loss of CH 3 is computed to be much more favorable than neutral ligand loss for La(CH 3 SO 2) 4 and Lu(CH 3 SO 2) 4-, whereas both channels are comparable in energy for Yb(CH 3 SO 2) 4-, in accord with the experiments. DFT results for fragmentation of Cu(CH 3 SO 2) 2 reveal that formation of the organometallic complex, Cu(CH 3 SO 2)(CH 3)-, is energetically most favorable, in agreement with contrasting fragmentation pathways of copper and lanthanide complexes.

show abstract

Lanthanide thermodynamic predictions

Cited by 16 publications

References 18 publications

Electrochemical behaviour of dysprosium(III) in LiF–CaF2 on Mo, Ni and Cu electrodes

Electrochemical behaviour of dysprosium(III) in LiF–CaF2 on Mo, Ni and Cu electrodes

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Electrospray production and collisional dissociation of lanthanide/methylsulfonyl anion complexes: Sulfur dioxide anion as a ligand

Contact Info

Product

Resources

About