Lithiumanionische Dicarbene oder Acetylide: Was ist im Namen enthalten?

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Март 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).

---

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

Organometallics, Год журнала: 2025, Номер unknown

Опубликована: Март 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.

Язык: Английский

---

Structural-N Engineered Frustrated Lewis Pairs in biomass-derived porous carbon for CO2 capture and conversion

Separation and Purification Technology, Год журнала: 2025, Номер unknown, С. 133346 - 133346

Опубликована: Май 1, 2025

Язык: Английский

---

Trapping an Elusive Phosphanyl‐Phosphaalumene

Chemistry - A European Journal, Год журнала: 2024, Номер 30(34)

Опубликована: Апрель 12, 2024

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

Язык: Английский

---

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

Chemical Society Reviews, Год журнала: 2024, Номер 53(19), С. 9874 - 9903

Опубликована: Янв. 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.

Язык: Английский

---

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

---

Using Gas Molecules to Assemble Value‐Added Materials through Dynamic Gas‐Bridged Bond

Macromolecular Rapid Communications, Год журнала: 2025, Номер unknown

Опубликована: Фев. 22, 2025

Abstract The conversion and utilization of greenhouse gases other polluting in a green way represents crucial strategy for developing C 1 chemistry mitigating the dual crises energy scarcity effect. As class polyatomic molecules with relatively simple structure, gas are directly involved assembled process as building blocks, converting them into polymer assemblies under mild low consumption, constructing recyclable functional materials, which is great significance to enrich block assembly promote sustainable value‐added gas. dynamic bridge new combining molecules, it provides possibility assembly. This perspective systematically introduces formation mechanism unique physicochemical properties bridge, discusses latest research progress gas‐bridged particular focus on three key aspects: gas‐regulated system, gas‐constructed efficient catalysis. Finally, critical challenges future directions materials based also highlighted.

Язык: Английский

---

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

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

Опубликована: Апрель 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.

Язык: Английский

---

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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(29), С. 19809 - 19817

Опубликована: Июль 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

Язык: Английский

---

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

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Сен. 18, 2024

ConspectusThe reductive conversion of carbon dioxide (CO

Язык: Английский

---