Formation, Structure and Reactivity of a Beryllium(0) Complex with Mg^δ+−Be^δ− Bond Polarization

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(35)

Опубликована: Май 31, 2024

Attempts to create a novel Mg-Be bond by reaction of [(

Язык: Английский

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Reductive Dimerization of Alkenes and Allenes Enabled by Photochemically Activated Zinc–Zinc Bonded Compounds

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19590 - 19598

Опубликована: Июль 3, 2024

Metal radicals have shown versatile reactivity in modern synthetic chemistry. However, the use of zinc for molecular synthesis has been barely explored. Here, we show that a transient radical can be formed through photoactivation zinc-zinc bonded compound, which is able to mediate selective dimerization alkenes and allenes. Treatment dizinc compounds [

Язык: Английский

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Multielectron Reduction of Nitrosoarene via Aluminylene-Silylene Cooperation

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Окт. 17, 2024

The cooperative effects of main-group elements pave the way for novel chemical transformations. However, potential bimetallic complexes featuring most abundant aluminum and silicon remains largely unexplored. In this study, we present synthesis characterization bis(silylene)-stabilized aluminylene

Язык: Английский

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Structural Snapshots of Reversible Carbon Dioxide Capture and (De)oxygenation at Group 14 Diradicaloids

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 8, 2024

Although diradicals should exhibit a rather small reaction barrier as compared to closed-shell species for activating kinetically inert molecules, the activation and functionalization of carbon dioxide with stable main-group remain virtually unexplored. In this work, we present thorough study on CO2 activation, reversible capture, (de)oxygenation mediated by Group 14 singlet (i.e., diradicaloids) [(ADC)E]2 (E = Si, Ge, Sn) based an anionic dicarbene (ADC) framework (ADC PhC{N(Dipp)C}2; Dipp 2,6-iPr2C6H3). readily undergo [4 + 2]-cycloadditions result in barrelene-type bis-metallylenes [(ADC)E]2(OC═O). The addition is E Ge; thus, detaches under vacuum or at elevated temperature regenerates [(ADC)Ge]2. [(ADC)Sn]2(OC═O) isolable but deoxygenates additional form [(ADC)Sn]2(O2CO) CO. [(ADC)Si]2(OC═O) extremely reactive could not be isolated detected it spontaneously reacts further yield elusive monomeric Si(IV) oxides [(ADC)Si(O)]2(COn) carbonates [(ADC)Si(CO3)]2(COn) (n 1 2) via CO2. molecular structures all compounds have been established X-ray diffraction, mechanistic insight their formation has suggested DFT calculations.

Язык: Английский

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Facile, Reversible Hydrogen Activation by Low-Coordinate Magnesium Oxide Complexes

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 28, 2025

New approaches to achieve facile and reversible dihydrogen activation are of importance for synthesis, catalysis, hydrogen storage. Here we show that low-coordinate magnesium oxide complexes [{(RDipnacnac)Mg}2(μ-O)] 1, with RDipnacnac = HC(RCNDip)2, Dip 2,6-iPr2C6H3, R Me (1a), Et (1b), iPr (1c), readily react under mild conditions afford mixed hydride-hydroxide [{(RDipnacnac)Mg}2(μ-H)(μ-OH)] 4. Dehydrogenation 4 is strongly dependent on remote ligand substitution can be achieved by simple vacuum-degassing 4c (R iPr) regain 1c. Donor addition also releases affords donor adducts complexes. Computational studies suggest the mechanism involves nucleophilic attack an lone pair at a weakly bound H2···Mg complex in SN2-like manner induces heterolytic cleavage yield MgOH MgH unit. Alternative synthetic routes into 4b from hydride have been investigated ability 1 or act as catalysts hydrogenation 1,1-diphenylethene (DPE) has tested.

Язык: Английский

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Reductive Coupling of Carbon Monoxide by an Anionic Calcium Hydride: A Computational Mechanistic Study

Organometallics, Год журнала: 2025, Номер unknown

Опубликована: Фев. 20, 2025

Язык: Английский

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Overview on Low-oxidation-state Alkaline Earth Organometallic Chemistry

Acta Chimica Sinica, Год журнала: 2025, Номер 83(2), С. 139 - 139

Опубликована: Янв. 1, 2025

Язык: Английский

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Manipulation of Solvent Donor Effects to Overcome the Calcium Schlenk Equilibrium

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 16, 2025

Synthetic access toward well-defined, monomeric s-block metal complexes is mired with chemical challenges, primarily attributed to the formation of homoleptic promoted by Schlenk equilibrium. Ligand redistribution significantly pronounced for heavier metals, such as calcium, which form bischelate readily through traditional synthetic routes transmetalation, amination, and ligand exchange. Mechanistic investigation each these phenoxyimine (ONN) ligands was explored ascertain fundamental parameters promote formation. Donor effects from coordinated solvent proved be deleterious, in an effort circumvent bischelation, a new calcium bisamide, {Ca[N(SiMe3)2]2(diox)2}∞, synthesized characterized coordination polymer unique square planar geometry, rarely seen group 2 complexes. Amination {Ca[N(SiMe3)2]2(diox)2}∞ found shift equilibrium favor heteroleptic species, allowing characterization calcium-amido complexes: [ONN1Ca-N(SiMe3)2]2(diox) [ONN3Ca-N(SiMe3)2(diox)]∞. Subsequent studies showed that exchange isolated dioxane THF notably shortened stability complex solution. Although steric have previously been regarded key stabilization complexes, it equally important consider donor ability achieve longer-lived heavy

Язык: Английский

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Reductive Cyclotrimerization of CO and Isonitriles with a Highly Reactive CaI Synthon

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A strongly reducing Ca I synthon releases N 2 and two electrons for the reductive C–C coupling of CO RNC.

Язык: Английский

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Synthesis and Characterization of Bulky 1,3‐Diamidopropane Complexes of Group 2 Metals (Be ‒ Sr)

Chemistry - An Asian Journal, Год журнала: 2024, Номер 19(15)

Опубликована: Май 18, 2024

Reaction of lithium 1,3-diamidopropane Li

Язык: Английский

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