Electromotive force measurements on solutions of rare earth metals in their molten halides. I. The cerium-cerium chloride, praseodymium-praseodymium chloride, and neodymium-neodymium chloride solutions

Bronstein, H. R.

doi:10.1021/j100725a024

Cited by 16 publications

(3 citation statements)

References 5 publications

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“…Hence, it was expected that +2 ions of the other metals, La, Ce, Pr, Gd, Tb, Ho, Er, and Lu, would only be accessible transiently under special conditions. Such species had been reported in gas-phase atomic spectra, , in ion cyclotron resonance studies, − in spectroscopic studies of Ln 3+ ions doped into CaF 2 and treated with γ radiation, and in electrochemical experiments in molten salts ,, and THF . All of these studies suggested that these ions would be too reactive to isolate in molecular species.…”

Section: Introductionmentioning

confidence: 94%

Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States

2016

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A fundamental aspect of any element is the range of oxidation states accessible for useful chemistry. This tutorial describes the recent expansion of the number of oxidation states available to the rare-earth and actinide metals in molecular complexes that has resulted through organometallic chemistry involving the cyclopentadienyl ligand. These discoveries demonstrate that the cyclopentadienyl ligand, which has been a key component in the development of organometallic chemistry since the seminal discovery of ferrocene in the 1950s, continues to contribute to the advancement of science. Background information on the rare-earth and actinide elements is presented, as well as the sequence of events that led to these unexpected developments in the oxidation state chemistry of these metals.

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Section: Introductionmentioning

confidence: 94%

Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States

2016

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“…Depressions of the freezing points of liquid RX 3 by added R have been found to be generally consistent with the formation of R 2+ cations [19,28,37,38]. EMF studies on melts of Ce, Pr, Nd in their trichlorides also support the formation of the dipositive cations [39]. Doping Ce into solid NdCl 2x phases can also be achieved to an extent that requires some Ce 2+ be present [5].…”

Section: Observed Phasesmentioning

confidence: 65%

Exploratory synthesis of reduced rare-earth-metal halides, chalcogenides, intermetallics

Corbett

2006

Journal of Alloys and Compounds

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“…其中, 只有铕、镱、钐这三种经典低价稀土金属有氟、氯、溴、碘四种二卤化物, 而非经典低价稀土铥、镝、钕有氯、溴、碘三种二卤化物, 至于其他非传统低价稀土金属则仅存在二碘化物(表5) [106] . ; 对于较难被还原的稀土金属, 利用稀土金属与稀土三卤化物进行归中反应是主要的合成路径 [111,118] ; 利用碱金属或碱土金属, 通过金属热还原法也可得到相应的目标产物, 这种方法还可能得到稀土金属、碱金属或碱土金属、卤离子的三元化合物 [112,119] . Bochkarev和Evans等域在晶格的导带中, 表现为正三价的稀土离子 [112] .…”

Section: 这一电子结构与非传统低价稀土金属分子配合物中二价稀土金属离子具有4funclassified

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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Electromotive force measurements on solutions of rare earth metals in their molten halides. I. The cerium-cerium chloride, praseodymium-praseodymium chloride, and neodymium-neodymium chloride solutions

Cited by 16 publications

References 5 publications

Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States

Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States

Exploratory synthesis of reduced rare-earth-metal halides, chalcogenides, intermetallics

Chemistry of non-traditional oxidation states of rare earth metals

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