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

Advanced Science, Journal Year: 2023, Volume and Issue: 11(5)

Published: Nov. 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.

Language: Английский

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Bis‐Silylene‐Supported Aluminium Atoms with Aluminylene and Alane Character

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 18, 2024

Abstract The suitability of electron‐rich bis‐silylenes, specifically the neutral chelating [Si II (Xant)Si ] ligand (Si =PhC(N t Bu) 2 Si, Xant=9,9‐dimethylxanthene) and anionic (N Acrid )Si )] − pincer =2,7,9,9‐tetramethylacridane), has been successfully probed to stabilize monovalent bis‐silylene‐supported aluminium complexes (aluminylenes). At first, unprecedented aluminium(III) iodide precursors ]AlI + I 1 )]AlI were synthesized using AlI 3 or )]Li(OEt )], respectively, structurally characterized. While reduction with KC 8 led merely unidentified products, dehalogenation afforded dimer desired {[Si )]Al:} aluminylene a four‐membered Si IV Al III ring. Remarkably, proposed intermediates ]Al could be produced through reaction Collman's reagent, K Fe(CO) 4 , trapped as :→Fe(CO) 5 6 respectively. is stable in solution, loses one CO solution afford silylene‐ aluminylene‐coordinated iron(0) complex 7 from an intramolecular substitution reaction. electronic structures novel compounds investigated by Density Functional Theory calculations.

Language: Английский

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Multielectron Reduction of Nitrosoarene via Aluminylene-Silylene Cooperation

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

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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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Arene extrusion as an approach to reductive elimination at boron: Implication of carbene-ligated haloborylene as a transient reactive intermediate

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Herein, we report boron-centered reductive elimination reactions to afford cyclic(alkyl)(amino) carbene (CAAC)-ligated chloroborylene and bromoborylene.

Language: 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, Journal Year: 2023, Volume and Issue: 30(5)

Published: Nov. 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.

Language: Английский

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

European Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 26(18)

Published: April 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.

Language: Английский

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Cooperative Activation of Small Molecules by Base-Stabilized Borylenes

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(23), P. 9063 - 9076

Published: June 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.

Language: Английский

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Geometrically Constrained Organoboron Species as Lewis Superacids and Organic Superbases

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(36)

Published: July 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.

Language: Английский

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