Actinide Endohedral and Exohedral Cubic Siloxanes: An(IV)@(HSiO1.5)8 and An(IV)&amp;(RSiO1.5)8 (An = U, Np, Pu; R = H, Cl, OH)

Duan, Meigang; Li, Peng; Zhao, Huifeng; Wu, Jizhou; Li, Yuqing; Li, Wenliang; Fu, Yongming; Xie, Feng; Ma, Jie

doi:10.1002/ejic.201900952

Cited by 2 publications

(2 citation statements)

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“…13 Recently, a series of actinide (uranium, neptunium, and plutonium) metallasilsesquioxanes were theoretically predicted, showing a prospect for the disposal of radioactive actinides. 14 The most popular synthetic approaches to cagelike metallasilsesquioxanes include the "synthon method" with hexameric Si 6 15a,b and heptameric Si 7 , 15c−e cyclic Si 4 , 15f or individual 15g,h silanols as starting reagents. An alternative approach implies a self-assembly with RSi(O)O − siloxanolate 15i,j units.…”

Section: ■ Introductionmentioning

confidence: 99%

Cu₆- and Cu₈-Cage Sil- and Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity

et al. 2021

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This study reports intriguing features in the self-assembly of cage copper(II) silsesquioxanes in the presence of air. Despite the wide variation of solvates used, a series of prismatic hexanuclear Cu 6 cages (1−5) were assembled under mild conditions. In turn, syntheses at higher temperatures are accompanied by side reactions, leading to the oxidation of solvates (methanol, 1-butanol, and tetrahydrofuran). The oxidized solvent derivatives then specifically participate in the formation of copper silsesquioxane cages, allowing the isolation of several unusual Cu 8 -based (6 and 7) and Cu 6 -based (8) complexes. When 1,4-dioxane was applied as a reaction medium, deep rearrangements occurred (with a total elimination of silsesquioxane ligands), causing the formation of mononuclear copper(II) compounds bearing oxidized dioxane fragments (9 and 11) or a formate-driven 1D coordination polymer (10). Finally, a "directed" self-assembly of sil-and germsesquioxanes from copper acetate (or formate) resulted in the corresponding acetate (or formate) containing Cu 6 cages (12 and 13) that were isolated in high yields. The structures of all of the products 1−13 were established by singlecrystal X-ray diffraction, mainly based on the use of synchrotron radiation. Moreover, the catalytic activity of compounds 12 and 13 was evaluated toward the mild homogeneous oxidation of C 5 −C 8 cycloalkanes with hydrogen peroxide to form a mixture of the corresponding cyclic alcohols and ketones.

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Section: ■ Introductionmentioning

confidence: 99%

Cu₆- and Cu₈-Cage Sil- and Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity

et al. 2021

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“…29 By design, partly condensed polyhedral silsesquioxanes can be also regarded as versatile ligands for the construction of various cagelike metallacomplexes. 30−38 These intriguing compounds attract significant interest for the potential removal of radioactive elements, 39 fabrication of flame retardants, 40−45 biomedical agents, 46 luminescent materials, 47,48 or molecular magnets. 49 Magnetic studies revealed rare cases of singlemolecule magnets (SMMs), 48,50 spin glass, 51 or spin−flip transition 52 effects.…”

Section: ■ Introductionmentioning

confidence: 99%

Acetone Factor in the Design of Cu₄-, Cu₆-, and Cu₉-Based Cage Coppersilsesquioxanes: Synthesis, Structural Features, and Catalytic Functionalization of Alkanes

et al. 2022

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The present study describes a new feature in the self-assembly of cagelike copperphenylsilsesquioxanes: the strong influence of acetone solvates on cage structure formation. By this simple approach, a series of novel tetra-, hexa-, or nonacoppersilsesquioxanes were isolated and characterized. In addition, several new complexes of Cu4 or Cu6 nuclearity bearing additional nitrogen-based ligands (ethylenediamine, 2,2′-bipyridine, phenanthroline, bathophenanthroline, or neocuproine) were produced. Single-crystal X-ray diffraction studies established molecular architectures of all of the synthesized products. Several coppersilsesquioxanes represent a novel feature of cagelike metallasilsesquioxane (CLMS) in terms of molecular topology. A Cu4–silsesquioxane complex with ethylenediamine (En) ligands was isolated via the unprecedented self-assembly of a partly condensed framework of silsesquioxane ligands, followed by the formation of a sandwich-like cage. Two prismatic Cu6 complexes represent the different conformersregular and elliptical hexagonal prisms, “cylinders”, determined by the different orientations of the coordinated acetone ligands (“shape-switch effect”). A heterometallic Cu4Na4-sandwich-like derivative represents the first example of a metallasilsesquioxane complex with diacetone alcohol ligands formed in situ due to acetone condensation reaction. As a selected example, the compound [(Ph6Si6O11)2Cu4En2]·(acetone)2 was explored in homogeneous oxidation catalysis. It catalyzes the oxidation of alkanes to alkyl hydroperoxides with hydrogen peroxide and the oxidation of alcohols to ketones with tert-butyl hydroperoxide. Radical species take part in the oxidation of alkanes. Besides, [(Ph6Si6O11)2Cu4En2]·(acetone)2 catalyzes the mild oxidative functionalization of gaseous alkanes (ethane, propane, n-butane, and i-butane). Two different model reactions were investigated: (1) the oxidation of gaseous alkanes with hydrogen peroxide to give a mixture of oxygenates (alcohols, ketones, or aldehydes) and (2) the carboxylation of C n gaseous alkanes with carbon monoxide, water, and potassium peroxodisulfate to give C n+1 carboxylic acids (main products), along with the corresponding C n oxygenates. For these reactions, the effects of acid promoter, reaction time, and substrate scope were explored. As expected for free-radical-type reactions, the alkane reactivity follows the trend C2H6 < C3H8 < n-C4H10 < i-C4H10. The highest total product yields were observed in the carboxylation of i-butane (up to 61% based on i-C4H10). The product yields and catalyst turnover numbers (TONs) are remarkable, given an inertness of gaseous alkanes and very mild reaction conditions applied (low pressures, 50–60 °C temperatures).

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Actinide Endohedral and Exohedral Cubic Siloxanes: An(IV)@(HSiO_1.5)₈ and An(IV)&(RSiO_1.5)₈ (An = U, Np, Pu; R = H, Cl, OH)

Abstract: Actinide metallasilsesquioxanes and their distinctive bonding properties have received an increased attention due to their potential value in advanced nuclear science and biomedicine. Herein, we have proposed a new class of endohedral

Cited by 2 publications

References 72 publications

Cu₆- and Cu₈-Cage Sil- and Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity

Cu₆- and Cu₈-Cage Sil- and Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity

Acetone Factor in the Design of Cu₄-, Cu₆-, and Cu₉-Based Cage Coppersilsesquioxanes: Synthesis, Structural Features, and Catalytic Functionalization of Alkanes

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Actinide Endohedral and Exohedral Cubic Siloxanes: An(IV)@(HSiO1.5)8 and An(IV)&(RSiO1.5)8 (An = U, Np, Pu; R = H, Cl, OH)

Abstract: Actinide metallasilsesquioxanes and their distinctive bonding properties have received an increased attention due to their potential value in advanced nuclear science and biomedicine. Herein, we have proposed a new class of endohedral

Cited by 2 publications

References 72 publications

Cu6- and Cu8-Cage Sil- and Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity

Cu6- and Cu8-Cage Sil- and Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity

Acetone Factor in the Design of Cu4-, Cu6-, and Cu9-Based Cage Coppersilsesquioxanes: Synthesis, Structural Features, and Catalytic Functionalization of Alkanes

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Actinide Endohedral and Exohedral Cubic Siloxanes: An(IV)@(HSiO_1.5)₈ and An(IV)&(RSiO_1.5)₈ (An = U, Np, Pu; R = H, Cl, OH)

Cu₆- and Cu₈-Cage Sil- and Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity

Cu₆- and Cu₈-Cage Sil- and Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity

Acetone Factor in the Design of Cu₄-, Cu₆-, and Cu₉-Based Cage Coppersilsesquioxanes: Synthesis, Structural Features, and Catalytic Functionalization of Alkanes