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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An N-Phosphinoamidinato Borasilenide: A Vinyl Anion Containing a B=Si Double Bond

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

An N -phosphinoamidinato potassium borasilenide containing an anionic SiB double bond is a versatile building block for transferring BSi or B/Si atoms into inorganic and organic substrates.

Язык: Английский

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Copper-PMHS System-Enabled Reductive Cyclization of o-Aminobenzamides with CO₂ as a Single-Carbon Synthon

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 18, 2025

Chemical utilization of carbon dioxide (CO2) has emerged as a sustainable access for synthesizing high-value chemicals. Continuously designing the more practical reaction systems is large importance. Herein, an unprecedented and powerful copper-PMHS reductive system o-aminobenzamides with CO2 disclosed. Synthetically, diverse range quinazolinones (>70 examples) are rapidly assembled excellent functional group tolerance in good yields. Moreover, building other types heterocycles such benzothiazoles benzimidazoles also allowable. Mechanistically, differing from reported carbonylation cases, this finding represents scarce example single-carbon atom synthon PMHS system.

Язык: Английский

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Isolation of Silylene-Ligated Plumbyliumylidene and Diplumbyne

Organometallics, Год журнала: 2025, Номер unknown

Опубликована: Март 19, 2025

Язык: Английский

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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

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Isolation of an Anionic Dicarbene Embedded Sn₂P₂ Cluster and Reversible CO₂ Uptake

Advanced Science, Год журнала: 2023, Номер 11(5)

Опубликована: Ноя. 28, 2023

Abstract Decarbonylation of a cyclic bis‐phosphaethynolatostannylene [(ADC)Sn(PCO)] 2 based on an anionic dicarbene framework (ADC = PhC{N(Dipp)C} ; Dipp 2,6‐ i Pr C 6 H 3 ) under UV light results in the formation Sn P cluster compound [(ADC)SnP] as green crystalline solid. The electronic structure is analyzed by quantum‐chemical calculations. At room temperature, reversibly binds with CO and forms [(ADC) {SnOC(O)P}SnP]. enables catalytic hydroboration reacts elemental selenium Fe (CO) 9 to afford {Sn(Se)P }SnSe] [(ADC)Sn{Fe(CO) 4 }P] , respectively. All compounds are characterized multinuclear NMR spectroscopy their solid‐state molecular structures determined single‐crystal X‐ray diffraction.

Язык: Английский

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Quo Vadis CO₂ Activation: Catalytic Reduction of CO₂ to Methanol Using Aluminum and Gallium/Carbon‐based Ambiphiles

Chemistry - A European Journal, Год журнала: 2023, Номер 30(5)

Опубликована: Ноя. 21, 2023

Abstract We report on so‐called “hidden FLPs” (FLP: frustrated Lewis pair) consisting of a phosphorus ylide featuring group 13 fragment in the ortho position phenyl ring scaffold to form five‐membered structures. Although formation acid/base adducts was observed solid state, most title compounds readily react with carbon dioxide provide stable insertion products. Strikingly, 0.3–3.0 mol% reported aluminum and gallium/carbon‐based ambiphiles catalyze reduction CO 2 methanol satisfactory high selectivity yields using pinacol borane as stoichiometric equivalent. Comprehensive computational studies provided valuable mechanistic insights shed more light activity differences.

Язык: Английский

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Hydrogenation of Olefins Catalyzed by a Cobalt(I) Hydride Complex with N‐Heterocyclic Silylene

European Journal of Inorganic Chemistry, Год журнала: 2023, Номер 26(18)

Опубликована: Апрель 6, 2023

Abstract Herein, we report the synthesis, characterization, and reactivity of cobalt(I) complexes with an N ‐heterocyclic imino substituted silylene. The hydride complex exhibits high catalytic efficiency chemoselectivity as well good functional group compatibility in hydrogenation olefins.

Язык: Английский

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Cooperative Activation of Small Molecules by Base-Stabilized Borylenes

Inorganic Chemistry, Год журнала: 2023, Номер 62(23), С. 9063 - 9076

Опубликована: Июнь 2, 2023

Computational investigations were carried out using density functional theory (ωB97XD(toluene)/6-311+G*) on a series of base-stabilized borylenes to understand their ligand properties and potential toward the activation enthalpically strong E-H bonds (E = H, NH2, SiH2Ph, CH3) as well binding with small molecules such CO CNMe. The calculated reaction free energies barriers suggest ability hitherto unexplored carbene-stabilized not only split but also bind A detailed mechanistic study these bond processes reveals noninnocent behavior carbene moiety attached boron center, thereby leading cooperative splitting interest. CNMe was investigated by energy decomposition analysis (EDA) natural orbitals for chemical valence (NOCV), which gave appreciable interaction (ΔEint) values, indicating borylenes.

Язык: Английский

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Geometrically Constrained Organoboron Species as Lewis Superacids and Organic Superbases

Angewandte Chemie, Год журнала: 2023, Номер 135(36)

Опубликована: Июль 3, 2023

Abstract This report unveils an advancement in the formation of a Lewis superacid (LSA) and organic superbase by geometrical deformation organoboron species towards T‐shaped geometry. The boron dication [ 2 ] 2+ supported amido diphosphine pincer ligand features both large fluoride ion affinity (FIA>SbF 5 ) hydride (HIA>B(C 6 F 3 ), which qualifies it as hard soft LSA. unusual acidic properties are further showcased its ability to abstract from Et SiH AgSbF respectively, effectively catalyze hydrodefluorination, defluorination/arylation, well reduction carbonyl compounds. One two‐electron affords stable radical cation ]⋅ + borylene , respectively. former has extremely high spin density 0.798 e at atom, whereas latter compound been demonstrated be strong base (calcd. p K BH (MeCN)=47.4) theoretical experimental assessment. Overall, these results demonstrate geometric constraining empower central atom.

Язык: Английский

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