Ligand Design in Modern Lanthanide Chemistry

Mills, David P.; Liddle, Stephen T.

doi:10.1002/9781118839621.ch12

Cited by 11 publications

(17 citation statements)

References 182 publications

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“…23,24 In the interim, numerous trigonal pyramidal and planar Ln 3+ and Ln 2+ complexes have been accessed by using a combination of sterically demanding ligands and strict anaerobic conditions. 25,26 In contrast, there are only a handful of structurally characterised monomeric Ln 2+ complexes with only two formally monodentate ligands; the majority contain intramolecular p-arene contacts, 27 14,35 have additional electrostatic interactions between the ligand s-bonding frameworks and Ln 2+ centres. Ln 3+ complexes with only two monodentate ligands have remained elusive to date as more Lewis acidic Ln 3+ centres favour higher coordination numbers.…”

Section: Introductionmentioning

confidence: 99%

Electronic structures of bent lanthanide(III) complexes with two N-donor ligands

et al. 2019

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Low coordinate metal complexes can exhibit superlative physicochemical properties, but this chemistry is challenging for the lanthanides (Ln) due to their tendency to maximize electrostatic contacts in predominantly ionic bonding regimes. Although a handful of Ln 2+ complexes with only two monodentate ligands have been isolated, examples in the most common +3 oxidation state have remained elusive due to the greater electrostatic forces of Ln 3+ ions. Here, we report bent Ln 3+ complexes with two bis(silyl)amide ligands; in the solid state the Yb 3+ analogue exhibits a crystal field similar to its three coordinate precursor rather than that expected for an axial system. This unanticipated finding is in opposition to the predicted electronic structure for two-coordinate systems, indicating that geometries can be more important than the Ln ion identity for dictating the magnetic ground states of low coordinate complexes; this is crucial transferable information for the construction of systems with enhanced magnetic properties.

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Section: Introductionmentioning

confidence: 99%

Electronic structures of bent lanthanide(III) complexes with two N-donor ligands

et al. 2019

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“…Sm 还原化学的研究为后续非经典乃至非传统低价稀土金属的还原化学奠定了基础和比较的标杆 [25,35,38] . [156] . 1991年, Nief等 [176] 利用稀土金属单质钐和镱与C 相似的方法也可获得其他不同取代基、不同配位模式的磷杂环戊二烯类的配合物 [177] .…”

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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“…This step-change in RE chemistry was also propelled by the many advances in anaerobic manipulation techniques and ligand design, which in turn led to discoveries that challenged common assumptions and opened unexpected research avenues. 7 , 10 …”

Section: Introductionmentioning

confidence: 99%

Rare Earth Starting Materials and Methodologies for Synthetic Chemistry

Ortu

2022

Chem. Rev.

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The number of rare earth (RE) starting materials used in synthesis is staggering, ranging from simple binary metal-halide salts to borohydrides and “designer reagents” such as alkyl and organoaluminate complexes. This review collates the most important starting materials used in RE synthetic chemistry, including essential information on their preparations and uses in modern synthetic methodologies. The review is divided by starting material category and supporting ligands ( i.e. , metals as synthetic precursors, halides, borohydrides, nitrogen donors, oxygen donors, triflates, and organometallic reagents), and in each section relevant synthetic methodologies and applications are discussed.

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Ligand Design in Modern Lanthanide Chemistry

Cited by 11 publications

References 182 publications

Electronic structures of bent lanthanide(III) complexes with two N-donor ligands

Electronic structures of bent lanthanide(III) complexes with two N-donor ligands

Chemistry of non-traditional oxidation states of rare earth metals

Rare Earth Starting Materials and Methodologies for Synthetic Chemistry

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