Molecular Thorium Trihydrido Clusters Stabilized by Cyclopentadienyl Ligands

Chen, Runhai; Qin, Guorui; Li, Shihui; Edwards, Alison J.; Piltz, Ross O.; Rosal, Iker del; Maron, Laurent; Cui, Dongmei; Cheng, Jianhua

doi:10.1002/ange.202002303

Cited by 3 publications

(2 citation statements)

References 39 publications

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“…Our research interest is mainly focused on organoactinide-based catalysts, due to the unique characteristics of actinide metals such as their large ionic size, high oxophilicity, and ability to display high coordination numbers. − These characteristics influence their stoichiometric and catalytic behavior. − The significance of using actinides in catalysis reactions have grown tremendously in recent years by applying organoactinides as catalysts for the hydroboration of unsaturated C–N bond of pyridines and heterocyclic systems, carbodiimides, nitriles, and imines. − …”

Section: Introductionmentioning

confidence: 99%

Catalytic Hydroboration of Esters by Versatile Thorium and Uranium Amide Complexes

2021

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The challenging hydroboration of esters is achieved using simple uranium and thorium amides, U[N(SiMe3)2]3 and [(Me3Si)2N]2An[κ2-(N,C)-CH2Si(CH3)2N(SiMe3)] (An = Th or U) acting as precatalysts in the reaction with pinacolborane (HBpin). All three complexes showed impressive catalytic activities, reaching excellent yields. A large scope of esters was investigated including aliphatic, aromatic, and heterocyclic esters that were transformed cleanly to the corresponding hydroborated alcohols, which readily hydrolyzed to the free alcohols. Moreover, the actinide catalysts demonstrated unexpected high functional tolerance toward nitro, halide, cyano, and heteroaromatic functional groups. The reaction exhibited excellent selectivity toward the ester when additional double and triple unsaturated C–C bonds were present. Lactones and poly caprolactone have been successfully cleaved to the monomeric units, showing a great promise toward polymer degradation and recycling. Detailed kinetic studies are provided in order to determine the rate dependence on the concentration of catalyst, HBpin, and ester. A plausible mechanism is proposed based on stoichiometric reactions, DFT calculations, thermodynamic measurements, and deuterium-labeling studies.

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Section: Introductionmentioning

confidence: 99%

Catalytic Hydroboration of Esters by Versatile Thorium and Uranium Amide Complexes

2021

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“…It is of particular importance to note that in the case of hydride containing compounds, it can be critical to prove the location of the hydride via neutron diffraction and even a low resolution study can provide the necessary proof. In consequence of their publication with the chemistry, papers from KOALA are now submitted to and published in journals of the highest standing [4][5][6][7].…”

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confidence: 99%

Finding the Goldilocks zone for chemical crystallography via Laue single-crystal neutron diffraction – what have we learned from KOALA to improve KOALA 2.0?

Edwards¹,

Piltz²

2021

Acta Cryst Sect A

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KOALA is a single-crystal Laue neutron diffractometer standing at the end of guide position of the supermirror guide TG3 at the OPAL reactor, ANSTO. The instrument was initially modelled closely on VIVALDI[1], an instrument available in the user program at the ILL from 2001-2010. The elegantly simple concept of the instrument employs a cylindrical neutron sensitised image plate detector which is used to record a series of diffraction images from a suitable number of crystal positions to provide a sufficient data set from which valid model parameters can be derived to answer questions regarding material properties which cannot be adequately derived from more readily available methods, most particularly X-ray diffraction and more recently the hybrid methodology of quantum crystallography.

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Thorium- and Uranium-Mediated C–H Activation of a Silyl-Substituted Cyclobutadienyl Ligand

et al. 2022

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Cyclobutadienyl complexes of the f-elements are a relatively new yet poorly understood class of sandwich and half-sandwich organometallic compounds. We now describe cyclobutadienyl transfer reactions of the magnesium reagent [(η4-Cb'''')Mg(THF)3] (1), where Cb'''' is tetrakis(trimethylsilyl)cyclobutadienyl, toward thorium(IV) and uranium(IV) tetrachlorides. The 1:1 stoichiometric reactions between 1 and AnCl4 proceed with intact transfer of Cb'''' to give the half-sandwich complexes [(η4-Cb'''')AnCl(μ-Cl)3Mg(THF)3] (An = Th, 2; An = U, 3). Using a 2:1 reaction stoichiometry produces [Mg2Cl3(THF)6][(η4-Cb'''')An(η3-C4H(SiMe3)3-κ-(CH2SiMe2)(Cl)] (An = Th, [Mg2Cl3(THF)6][4]; An = U [Mg2Cl3(THF)6][5]), in which one Cb'''' ligand has undergone cyclometalation of a trimethylsilyl group, resulting in the formation of an An–C σ-bond, protonation of the four-membered ring, and an η3-allylic interaction with the actinide. Complex solution-phase dynamics are observed with multinuclear nuclear magnetic resonance spectroscopy for both sandwich complexes. A computational analysis of the reaction mechanism leading to the formation of 4 and 5 indicates that the cyclobutadienyl ligands undergo C–H activation across the actinide center.

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Molecular Thorium Trihydrido Clusters Stabilized by Cyclopentadienyl Ligands

Cited by 3 publications

References 39 publications

Catalytic Hydroboration of Esters by Versatile Thorium and Uranium Amide Complexes

Catalytic Hydroboration of Esters by Versatile Thorium and Uranium Amide Complexes

Finding the Goldilocks zone for chemical crystallography via Laue single-crystal neutron diffraction – what have we learned from KOALA to improve KOALA 2.0?

Thorium- and Uranium-Mediated C–H Activation of a Silyl-Substituted Cyclobutadienyl Ligand

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