From germolane to germylenes: a theoretical DFT study of thermal decomposition pathways and reactivity DOI
Ismail Badran

Journal of Coordination Chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 1 - 13

Published: Nov. 14, 2024

This study addresses the often-overlooked chemistry of germanium compared to extensively researched carbon and silicon. Using advanced DFT methods, we investigated thermal decomposition germolane (germacyclopentane). The suggested mechanisms include a 1,2-H shift 1,1-H2 elimination form pentacyclic germylene (1λ2-germolane). other pathway involves stepwise [3 + 2] cycloreversion diradical followed by ethene germirane. Under M062X/def2-TZVP level theory, activation barriers in terms Gibbs energy (ΔG‡298) for pathways were 240.9 236.3 kJ/mol, respectively. reaction energies (ΔG°298) initiative steps 102.9 96.2 indicating thermodynamic kinetic competition between two routes. Temperature dependence analysis from 300 1200 K reveals that dominates at higher temperatures is expected become spontaneous above 1000 K.

Language: Английский

Photocatalytic Germylation via Direct Hydrogen Atom Transfer DOI

Wenshan Wang,

Yan Liu,

Qiang Gao

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

Comprehensive Summary An innovative visible‐light‐driven direct hydrogen atom transfer ( d ‐HAT) of Ge–H bond has been developed, wherein the photoexcited 9,10‐phenanthraquinone PC HAT 9 ) serves as an efficient photocatalyst for generation germanium‐centered radicals from germanium hydrides including Ph 3 GeH, n Bu and 2 GeH . By employing hypervalent iodine reagents SOMOphiles, this protocol facilitates streamlined germylation through a mechanism involving germyl radical addition followed by β‐cleavage carboxyl to yield diverse array ethynyl‐, vinyl‐, nitrile‐, phenyl‐functionalized germanes. The methodological leap signifies noteworthy departure previous photocatalytic indirect i relying on combined usage SET with abstractors, which not only advances methodology creating in fashion but also provides access structurally novel pharmaceutically promising organogermanium compounds that are difficult synthesize routine methods.

Language: Английский

Citations

0
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
Catalytic Construction of C(sp3)‐Ge Bonds: Recent Advances and Future Perspectives DOI
Jia‐Lin Tu, Binbin Huang

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(22), P. 4618 - 4633

Published: Oct. 16, 2024

Abstract Germanium (Ge), a congener of carbon, possesses unique properties that hold extensive potential for applications across multiple domains. Recent years have seen significant progress in the development carbon‐germanium bond formation strategies, particularly those more challenging C( sp 3 )−Ge bonds. This review systematically summarizes recent advances forming methodologies, with particular emphasis on (1) versatility transition‐metals, including iron, nickel, copper, rhodium and palladium, as catalysts broadening reaction scope controlling selectivity; (2) powerfulness organic photocatalysis achieving mild selective formation, (3) sustainability catalytic electrosynthesis facilitating chemical oxidant‐/reductant‐ free conversions. Additionally, examples (4) non‐catalytic strategies are also discussed. The representative scopes, well mechanistic proposals, these protocols highlighted. Through an overview current state research, this aims to offer insights into construction bonds, provide perspectives future research directions address challenges.

Language: Английский

Citations

1
From germolane to germylenes: a theoretical DFT study of thermal decomposition pathways and reactivity DOI
Ismail Badran

Journal of Coordination Chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 1 - 13

Published: Nov. 14, 2024

This study addresses the often-overlooked chemistry of germanium compared to extensively researched carbon and silicon. Using advanced DFT methods, we investigated thermal decomposition germolane (germacyclopentane). The suggested mechanisms include a 1,2-H shift 1,1-H2 elimination form pentacyclic germylene (1λ2-germolane). other pathway involves stepwise [3 + 2] cycloreversion diradical followed by ethene germirane. Under M062X/def2-TZVP level theory, activation barriers in terms Gibbs energy (ΔG‡298) for pathways were 240.9 236.3 kJ/mol, respectively. reaction energies (ΔG°298) initiative steps 102.9 96.2 indicating thermodynamic kinetic competition between two routes. Temperature dependence analysis from 300 1200 K reveals that dominates at higher temperatures is expected become spontaneous above 1000 K.

Language: Английский

Citations

0