Organo-f-element bonding energetics. Large magnitudes of metal arene bond enthalpies in zero-valent lanthanide sandwich complexes

King, Wayne A.; Marks, Tobin J.; Anderson, David M.; Duncalf, David J.; Cloke, F. Geoffrey N.

doi:10.1021/ja00049a084

Cited by 66 publications

(30 citation statements)

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“…Cloke和Marks等 [271] [142,143] . 我国的黎乐民院士等 [272] 通过理论计算提出了6s→5d的电子跃迁能才是决定此类稀土金属芳烃配合物稳定性的关键, 即 6s→5d的电子跃迁能较低的稀土金属能够形成稳定的三明治型零价稀土金属芳烃配合物.…”

Section: 三明治型零价稀土金属芳烃配合物异乎寻常的稳定性引起了实验化学家与理论化学家的浓厚兴趣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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Section: 三明治型零价稀土金属芳烃配合物异乎寻常的稳定性引起了实验化学家与理论化学家的浓厚兴趣unclassified

Chemistry of non-traditional oxidation states of rare earth metals

Wang¹,

Huang²

2020

Sci. Sin.-Chim

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“…Arenes can serve as both neutral and anionic ligands in complexes with highly electropositive metals. 43 Lappert and co-workers isolated and structurally characterized several lanthanide benzene complexes with various degrees of benzene reduction. 19 Between 1987 and 1993, Cloke et al reported a series of sandwich rare-earth metal arene complexes with a formal oxidation state of zero for the metal.…”

Section: Anionic Six-membered Ring Arene Complexesmentioning

confidence: 99%

“…Therefore, the benzene 1,4-dianion is best described as an interrupted π-electron system, with strong σ bond character between C1/C4 and the lanthanide ions. [40][41][42][43] Typically, sterically demanding benzene derivatives, such as 1,3,5tri-tert-butylbenzene, were required to obtain stable products characterized as Ln(1,3,5-C 6 H 3 -Bu t 3 ) 2 . 45 The authors preferred the former because, at that time, a triply reduced benzene seemed implausible.…”

Section: Anionic Six-membered Ring Arene Complexesmentioning

confidence: 99%

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Rare-earth metal π-complexes of reduced arenes, alkenes, and alkynes: bonding, electronic structure, and comparison with actinides and other electropositive metals

Huang

Diaconescu

2015

Dalton Trans.

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Rare-earth metal complexes of reduced π ligands are reviewed with an emphasis on their electronic structure and bonding interactions. This perspective discusses reduced carbocyclic and acyclic π ligands; in certain categories, when no example of a rare-earth metal complex is available, a closely related actinide analogue is discussed. In general, rare-earth metals have a lower tendency to form covalent interactions with π ligands compared to actinides, mainly uranium. Despite predominant ionic interactions in rare-earth chemistry, covalent bonds can be formed with reduced carbocyclic ligands, especially multiply reduced arenes.

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“…In addition, de Matos introduced the "steric coordination number" for actinide complexes, which implies a pure ionic bonding model, and is based on the ligands cone angles [23]. Furthermore, the reactivity of actinide compounds can be further elucidated by using thermochemical studies, which allow for a prediction of new reaction pathways by taking into account the metal ligand bond disruption enthalpies [24][25][26][27][28][29][30]. It has been also shown that due to the high energy orbital impediment to undergo oxidative addition and reductive elimination reactions, catalytic processes mediated by neutral organoactinide complexes proceed via an ordered four-membered transition state (Scheme 1) [31].…”

Section: Introductionmentioning

confidence: 99%

Catalytic Organic Transformations Mediated by Actinide Complexes

2015

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This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field.

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Organo-f-element bonding energetics. Large magnitudes of metal arene bond enthalpies in zero-valent lanthanide sandwich complexes

Cited by 66 publications

References 0 publications

Chemistry of non-traditional oxidation states of rare earth metals

Chemistry of non-traditional oxidation states of rare earth metals

Rare-earth metal π-complexes of reduced arenes, alkenes, and alkynes: bonding, electronic structure, and comparison with actinides and other electropositive metals

Catalytic Organic Transformations Mediated by Actinide Complexes

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