Comparison of tetravalent cerium and terbium ions in a conserved, homoleptic imidophosphorane ligand field

Rice, Natalie; Popov, Ivan A.; Russo, Dominic R.; Gompa, Thaige P.; Ramanathan, Arun; Bacsa, John; Batista, Enrique R.; Yang, Ping; Pierre, Henry S. La

doi:10.1039/d0sc01414a

Cited by 42 publications

(71 citation statements)

References 52 publications

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“…Very recently, high‐energy‐resolution fluorescence detection X‐ray absorption spectroscopy (HERFD‐XAS) has been used to analyse a formal di‐cerium(IV) phenolate complex and confirmed mixed valency with considerable 4f 0 character [138] . In addition, the multiconfigurational ground state of formal Ce IV complexes stabilised by imidophosphorane ligands or imidophosphorane‐functionalised guanidinate ligands has been established through Ce L 3 ‐edge XANES studies [139–141] . Notably, the imidophosphorane Ce IV complexes exhibited the lowest reported relative proportion of Ce III Lf 1 character ( n f =0.38(2)).…”

Section: Spectroscopic Singularitiesmentioning

confidence: 99%

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Intermediate Valence States in Lanthanide Compounds

Tricoire

Mahieu

Simler

et al. 2021

Chemistry A European J

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Over more than 50 years, intermediate valence states in lanthanide compounds have often resulted in unexpected or puzzling spectroscopic and magnetic properties. Such experimental singularities could not be rationalised until new theoretical models involving multiconfigurational electronic ground states were established. In this minireview, the different singularities that have been observed among lanthanide complexes are highlighted, the models used to rationalise them are detailed and how such electronic effects may be adjusted depending on energy and symmetry considerations is considered. Understanding and tuning the ground‐state multiconfigurational behaviour in lanthanide complexes may open new doors to modular and unusual reactivities.

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Section: Spectroscopic Singularitiesmentioning

confidence: 99%

“…Notably, the imidophosphorane Ce IV complexes exhibited the lowest reported relative proportion of Ce III Lf 1 character ( n f =0.38(2)). However, some limits to the dominant two‐peak model in the analysis of the L 3 ‐edge XANES spectra of tetravalent lanthanides were presented [140] …”

Section: Spectroscopic Singularitiesmentioning

confidence: 99%

Intermediate Valence States in Lanthanide Compounds

Tricoire

Mahieu

Simler

et al. 2021

Chemistry A European J

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“…While it is also apparent that with an increased applied voltage, the redox peaks are increased which may be due to the exchange of electrons of carboxyl anions between terbium cations and GO carboxyl groups. 28,29 Although the rst reduction peak is increased, but the second reduction peak is decreased due to the exchange of electrons of epoxy ions between Tb 3+ and also the non-bonding electrons of GO which is responsible for the intercalation of electrochemically active Tb 3+ . Hence, the mesomeric effect of epoxy ions could support stable redox behaviour.…”

Section: Microscopy Studiesmentioning

confidence: 99%

Facile synthesis of Tb-decorated graphene oxide: electrochemical stability, hydrogen storage, and corrosion inhibition of Mg AZ13 alloy in 3.5% NaCl medium

et al. 2021

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“…四价铈给其他高价稀土金属提供了一个极佳的研究参照, 借助于对四价铈分子配合物的相对稳定性与氧化还原电势的测量, Schelter等 [69] 和La Pierre等 [70,71] 发现通过设计具有强σ和π给电子性的带负电荷的配体可以极好地稳定四价铈离子, 并极大地降低Ce , 特别地, 三(叔丁氧基)硅氧基配体可以同时稳定低价(二价铈) [104] 和高价(四价铈) [69] 的分子配合物. 由无水的碘化物TbI 3 出发, 与4当量的KOSi- [59] , 但足以说明铽的氧化态发生了变化.…”

Section: 气相unclassified

Chemistry of non-traditional oxidation states of rare earth metals

Wang¹,

Huang²

2020

Sci. Sin.-Chim

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The chemistry of rare-earth metals (Sc, Y and lanthanides) has been dominated by trivalent oxidation states, except for divalent europium, ytterbium, and samarium and tetravalent cerium. The lack of readily accessible oxidation states limits the participation of rare earth metals in redox chemistry. Therefore, expanding the oxidation states of rare earth metals and synthesizing molecular rare earth metal complexes of non-traditional oxidation states are not only the long-term goal sought by synthetic chemists but also the pre-requisite for developing redox chemistry mediated by rare earth metals. Recently, major breakthroughs have been achieved in this field. All rare earth metals, except radioactive promethium, have been shown to exist in divalent states in molecular complexes, while molecular complexes of tetravalent terbium and praseodymium have been synthesized for the first time. Judicious ligand design is key to stabilizing these non-traditional oxidation states of rare earth metals. Moreover, upon studying the electronic structures and bonding interactions of these complexes, it has been shown that the coordination environment has a non-negligible influence on the electron configuration of rare earth metals. In this review, we will first analyze the electron configuration of rare earth metals and introduce the history of pursuing oxidation states other than +3 for rare earth metals. Then we will show the recent advancement in expanding the non-traditional oxidation states of rare earth metals with a focus on molecular complexes of both high and low valent rare earth metals. At the end, we will provide perspectives and outlook for the future development of this field.

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Comparison of tetravalent cerium and terbium ions in a conserved, homoleptic imidophosphorane ligand field

Abstract: A redox pair of Ce4+ and Ce3+ complexes, isotypic to previously prepared Tb4+ and Tb3+ complexes, respectively, is reported to establish a comparative physical and spectroscopic analysis of tetravalent lanthanide ions.

Cited by 42 publications

References 52 publications

Intermediate Valence States in Lanthanide Compounds

Intermediate Valence States in Lanthanide Compounds

Facile synthesis of Tb-decorated graphene oxide: electrochemical stability, hydrogen storage, and corrosion inhibition of Mg AZ13 alloy in 3.5% NaCl medium

Chemistry of non-traditional oxidation states of rare earth metals

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