Lithiumanionische Dicarbene oder Acetylide: Was ist im Namen enthalten?

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Abstract Die zweifache Deprotonierung der C2‐arylierten 1,3‐Imidazoliumsalze ((IPr‐Ar)X ( 1 ‐Ar)X (IPr‐Ar=ArC{N(Dipp)CH} 2 ; Ar=Ph, 4‐Me NC 6 H 4 (DMP) oder 4‐PhC (Bp); Dipp=2,6‐ i Pr C 3 ) mit n BuLi liefert die sogenannten anionischen Dicarbene Li(ADC) ‐Ar) (ADC=ArC{N(Dipp)C} ). ‐Ar können zur Herstellung einer Vielzahl von Hauptgruppenheterocyclen verwendet werden, ihre Strukturen im Festkörper sind jedoch bisher unbekannt. hier berichteten Einkristallröntgenbeugungsstudien zeigen eine acetylidartige [ArC{N(Dipp)}(Dipp)NC≡CLi)] dimere =2) trimere =3) Molekularstruktur für ‐Ar. Umsetzung ‐Ph Et B führt zu dem monoanionischen Carben Li[(ADC)(BEt )] ‐Ph) einem schwach koordinierenden Anion, welches in dieselbe Moleküleinheit eingebettet ist. reagieren sofort CO und N O unter Bildung Ringschlussprodukte Li[(ADC)(CO ] 5 bzw. Li[(ADC)N O] ‐Ar).

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Attempts toward a Silyl-Stabilized Dicoordinate Borylene: Insertion of Carbon Dioxide into the B–Si Bond

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

Published: March 26, 2025

One-electron reduction of the carbene-stabilized borane (Me2-cAAC)B(Cl)2Si(SiMe3)3, 1, with potassium naphthalenide gave radical (Me2-cAAC)B(Cl)Si(SiMe3)3, 2. A subsequent one-electron 2 yielded dicoordinate borylene (Me2-cAAC)BSi(SiMe3)3, 3, which rapidly underwent intramolecular C-H activation to give cyclo-(Me2-cAAC)B(H)Si(SiMe3)3, 4, irrespective employed reaction conditions. Compound 3 could be stabilized as carbonyl complex (Me2-cAAC)B(CO)Si(SiMe3)3, 5, that 4 upon irradiation a UV light under CO2 atmosphere. In contrast, two-electron 1 an atmosphere mixture products (Me2-cAAC)B(Cl)(H)C(O)OSi(SiMe3)3, 6, separated and structurally characterized. 6 is rare example insertion into B-E (E = heavier main group element) bond in boron functions nucleophile, thereby mimicking transition metal-mediated carboxylation. The mechanism for formation from purported boryl anion intermediate [(Me2-cAAC)B(Cl)Si(SiMe3)3]-, -, was analyzed computationally.

Language: Английский

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Cooperative Heterobimetallic CO₂ Activation Involving a Mononuclear Aluminum(II) Intermediate

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

Published: April 3, 2025

Molecular chemistry of aluminum most commonly involves AlIII ions due to their noble gas electronic configurations. In contrast, the AlII is underexplored and may contain undiscovered reaction manifolds. Here, we report CO2 activation a transient intermediate supported by chelating, dianionic ligand investigate structure details mechanisms required access this reactivity. We found that heterobinuclear complex, (NON)Al-FeCp(CO)2 (1), undergoes Al-Fe bond homolysis at ambient conditions reveal [(NON)Al]•/[CpFe(CO)2]• radical pair in situ. The presence predominantly Al-centered spin density (i.e., an ion) within was established quantum-chemical calculations with experiments which scavengers (TEMPO, benzophenone) induce homolysis. Exposure 1 atmosphere resulted insertion into bond. This net 2-electron reduction process computationally modeled using functional theory direct dynamics simulations, revealing two 1-electron steps and, thus, depends on stabilization high-energy [CO2]•- coordination aluminum. mechanism for unexpected given canonical predisposition multielectron processes demonstrates possibility discovering new profiles earth-abundant elements unusual oxidation states.

Language: Английский

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Trapping an Elusive Phosphanyl‐Phosphaalumene

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(34)

Published: April 12, 2024

We describe our efforts to access a compound with an Al=P double bond by reaction of Al(Nacnac) towards [H

Language: Английский

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Experimental and computational aspects of molecular frustrated Lewis pairs for CO₂ hydrogenation: en route for heterogeneous systems?

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(19), P. 9874 - 9903

Published: Jan. 1, 2024

This review provides an overview of FLP chemistry in the field CO 2 hydrogenation, whichcovers both experimental and computational aspects, while ranging from homogeneous catalysis to recent heterogenisation strategies porous solids.

Language: 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, 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

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Use of Microwave Dielectric Spectroscopy for the In Actu Assessment of Frustrated Lewis Pair Encounter Complexes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 19809 - 19817

Published: July 16, 2024

Frustrated Lewis pairs (FLPs) offer an important and promising paradigm for main group catalysis. Reported here is the use of microwave dielectric spectroscopy

Language: Английский

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Advances and Roles of Oxygen Vacancies in Semiconductor Photocatalysts for Solar-Driven CO2 Reduction

Surfaces and Interfaces, Journal Year: 2024, Volume and Issue: 53, P. 104957 - 104957

Published: Aug. 23, 2024

Language: Английский

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Hydride Transfer-Based CO₂ Reduction Catalysis: Navigating Metal Hydride to Organic Hydride in the Catalytic Loop

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 18, 2024

ConspectusThe reductive conversion of carbon dioxide (CO

Language: Английский

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Dynamic Gas-Bridged Bond: An Opportunity of Fabricating Dynamic Assembled Materials with Gas

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(33), P. 43093 - 43101

Published: Aug. 8, 2024

Gas molecules, as a family of unique polyatomic building blocks, have long been considered hard to involve in molecular assembly or construct assembled materials due their structural simplicity yet paucity defined interacting sites. To solve this non-trivial challenge, core idea is break the limit current ways bonding gas endowing them with new modes interactions that match basic requirements assembly. In recent years, concept, named dynamic gas-bridged bond (DGB), has emerged, which allows for molecules constitute bridging structure between other blocks aid frustrated Lewis pairs. This makes it possible harness supramolecular manner. Herein, perspective discusses distinct natures DGBs and manifests particular functions various fields, including control molecular/polymeric self-assembly nanostructures, creation multidimensional materials, recyclable catalysts. The future research direction challenges chemistry toward gas-programmed gas-constructed adaptive are highlighted.

Language: Английский

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