Reactivity of Strontium Hydride Supported by the Superbulky Hydrotris(pyrazolyl)borate Ligand DOI Creative Commons
Xun Gong, Xianghui Shi, Peng Deng

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 18, 2024

Hydrogenolysis of [(Tp

Formation, Structure and Reactivity of a Beryllium(0) Complex with Mgδ+−Beδ− Bond Polarization DOI Creative Commons

Chantsalmaa Berthold,

Johannes Maurer,

Lukas Klerner

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(35)

Published: May 31, 2024

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

Language: Английский

Citations

10
Reductive Dimerization of Alkenes and Allenes Enabled by Photochemically Activated Zinc–Zinc Bonded Compounds DOI

Shuilian Xu,

Qiujie Wang, Thayalan Rajeshkumar

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19590 - 19598

Published: July 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 [

Language: Английский

Citations

3
Multielectron Reduction of Nitrosoarene via Aluminylene-Silylene Cooperation DOI
Xi Chen, Dezhi Yang,

Fanshu Cao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 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

Language: Английский

Citations

3
Structural Snapshots of Reversible Carbon Dioxide Capture and (De)oxygenation at Group 14 Diradicaloids DOI
Falk Ebeler,

Beate Neumann,

Hans‐Georg Stammler

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 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.

Language: Английский

Citations

3
Facile, Reversible Hydrogen Activation by Low-Coordinate Magnesium Oxide Complexes DOI Creative Commons

Simon Thompson,

Stuart Burnett,

Rochelle Ferns

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

Citations

0
Reductive Coupling of Carbon Monoxide by an Anionic Calcium Hydride: A Computational Mechanistic Study DOI
Alireza Ariafard, Farshad Shiri, Robert Stranger

et al.

Organometallics, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 20, 2025

Language: Английский

Citations

0
Overview on Low-oxidation-state Alkaline Earth Organometallic Chemistry DOI
Rong Chen, Wei Wei,

Baosheng

et al.

Acta Chimica Sinica, Journal Year: 2025, Volume and Issue: 83(2), P. 139 - 139

Published: Jan. 1, 2025

Language: Английский

Citations

0
Manipulation of Solvent Donor Effects to Overcome the Calcium Schlenk Equilibrium DOI
Kaitlyn M. Birkhoff, I-Hsin Lin,

Sam Yruegas

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 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

Language: Английский

Citations

0
Reductive Cyclotrimerization of CO and Isonitriles with a Highly Reactive CaI Synthon DOI Creative Commons
Stefan Thum, Jonathan Mai, Martin Schmidt

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

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

Language: Английский

Citations

0
Synthesis and Characterization of Bulky 1,3‐Diamidopropane Complexes of Group 2 Metals (Be ‒ Sr) DOI Creative Commons
Dat T. Nguyen, Christoph Helling, Cameron Jones

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: 19(15)

Published: May 18, 2024

Reaction of lithium 1,3-diamidopropane Li

Language: Английский

Citations

2