Insertion of CO₂and CS₂into Bi–N bonds enables catalyzed CH-activation and light-induced bismuthinidene transfer

Chemical Science, Год журнала: 2023, Номер 14(19), С. 5214 - 5219

Опубликована: Янв. 1, 2023

CO 2 and CS cleanly insert into Bi–N bonds of cationic bismuth amides. The insertion products are metastable undergo either elimination along with CH activation or light-induced bismuth( i ) triflate C–S bond formation.

Язык: Английский

---

Conjugate Aminocyclization Catalyzed by a Bismuthinidene

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер unknown

Опубликована: Окт. 4, 2023

Abstract We disclose how an N , C ‐bismuthinidene is able to promote intramolecular conjugate amination that affords cyclic carbamates in 91–97% yields. The reaction proceeds at room temperature short times, requiring a remarkably low loading of bismuth(I) complex (0.1 mol%) without the need additional Brønsted base. Preliminary mechanistic studies suggest takes place through polar pathway involving addition nucleophilic bismuthinidene, followed by aza‐Michael reaction.

Язык: Английский

---

CH Activation of Cationic Bismuth Amides: Heteroaromaticity, Derivatization, and Lewis Acidity

Inorganic Chemistry, Год журнала: 2021, Номер 60(24), С. 19086 - 19097

Опубликована: Ноя. 24, 2021

Cationization of Bi(NPh2)3 has recently been reported to allow access single- and double-CH activation reactions, followed by selective transformation Bi-C into C-X functional groups (X = electrophile). Here we show that this approach can successfully be transferred a range bismuth amides with two aryl at the nitrogen, Bi(NRaryl2)3. Exchange one nitrogen-bound group for an alkyl substituent gave first example homoleptic amide mixed aryl/alkyl substitution pattern Bi(NPhiPr)3. This compound is susceptible N-N radical coupling in its neutral form also undergoes CH when transformed cationic species. The second blocked due absence moiety nitrogen. Lewis acidity compared species "[Bi(aryl)(amide)(L)n]+" "[Bi(aryl)2(L)n]+" based on (modified) Gutmann-Beckett method (L tetrahydrofuran or pyridine). heteroaromatic character [Bi(C6H3R)2NH(triflate)] compounds, which are iso-valence-electronic anthracene, investigated theoretical methods. Analytical methods used work include nuclear magnetic resonance spectroscopy, single-crystal X-ray diffraction, mass spectrometry, density theory calculations.

Язык: Английский

---

Dihalo bismuth cations: unusual coordination properties and inverse solvent effects in Lewis acidity

Chemical Communications, Год журнала: 2022, Номер 58(70), С. 9826 - 9829

Опубликована: Янв. 1, 2022

A series of well-defined cationic hepta-coordinate bismuth halides [BiX2(py)5][B(3,5-(CF3)2-C6H3)4] (X = Cl, Br, I), stabilized only by substitutionally labile solvent molecules, were synthesized and fully characterized. Their apparent D5h symmetry with a lone pair at the central atom is unprecedented for main group compounds. The potential BiX3 to show unexpectedly high Lewis acidities in moderately polar solvents likely due formation [BiX2(solv)5]+ related ionic species.

Язык: Английский

---

Isolation and characterization of bis(silylene)-stabilized antimony(I) and bismuth(I) cations

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Май 23, 2023

Monovalent group 15 cations L2Pn + (L = σ-donor ligands, Pn N, P, As, Sb, Bi) have attracted significant experimental and theoretical interest because of their unusual electronic structures growing synthetic potential. Herein, we describe the synthesis a family antimony(I) bismuth(I) supported by bis(silylene) ligand [(TBDSi2)Pn][BArF4] (TBD 1, 8, 10, 9-triazaboradecalin; ArF 3,5-CF3-C6H3; (2); Bi, (3)). The 2 3 been unambiguously characterized spectroscopically X-ray diffraction analysis DFT calculations. They feature bis-coordinated Sb Bi atoms which exhibit two lone pairs electrons. reactions with methyl trifluoromethane sulfonate provide approach for preparation dicationic antimony(III) bismuth(III) complexes. Compounds serve as 2e donors to 6 metals (Cr, Mo), giving rise ionic antimony bismuth metal carbonyl complexes 6-9.

Язык: Английский

---

The Dimethylbismuth Cation: Entry Into Dative Bi−Bi Bonding and Unconventional Methyl Exchange

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(46), С. 24388 - 24394

Опубликована: Авг. 11, 2021

The isolation of simple, fundamentally important, and highly reactive organometallic compounds remains among the most challenging tasks in synthetic chemistry. detailed characterization such is key to discovery novel bonding scenarios reactivity. dimethylbismuth cation, [BiMe

Язык: Английский

---

Bismuth species in the coordination sphere of transition metals: synthesis, bonding, coordination chemistry, and reactivity of molecular complexes

Dalton Transactions, Год журнала: 2021, Номер 50(21), С. 7120 - 7138

Опубликована: Янв. 1, 2021

Bismuth species in the coordination sphere of transition metals show widely tunable bonding situations, impacting their stoichiometric and catalytic reactivity.

Язык: Английский

---

Bi particles with exposed (012) facet on 3D substrate as highly active and durable electrode for CO2 reduction to formate

Journal of CO2 Utilization, Год журнала: 2021, Номер 55, С. 101797 - 101797

Опубликована: Ноя. 13, 2021

Язык: Английский

---

Bismuth-based Lewis acidity

Advances in inorganic chemistry, Год журнала: 2023, Номер unknown, С. 237 - 260

Опубликована: Янв. 1, 2023

Язык: Английский

---

Theoretical Study on Bismuth(III) Catalysts for Synthesis of Phenylsulfonyl Fluoride: Reasons of Their Catalysis

ACS Catalysis, Год журнала: 2024, Номер 14(4), С. 2758 - 2774

Опубликована: Фев. 7, 2024

Bismuth(III) complex with diarylsulfone ligand (diAr-SO2) is a non-transition metal catalyst reported recently for the synthesis of arylsulfonyl fluorides. We investigated this catalytic reaction using DFT and SCS-MP2 calculations geometries energies, respectively. This occurs through transmetalation between (BF4)Bi(diAr-SO2) phenylboronic acid (PhB(OH)2), SO2 insertion into Bi–Ph bond (Ph)Bi(diAr-SO2), fluorination PhOSO group (PhOSO)Bi(diAr-SO2) by Selectfluor. The rate-determining step diAr-SO2 (CH3, CH3) (CF3, CF3) but either or CF3), where (R1, R2) means has R1 R2 substituents on its aryl groups. activation energy (ΔG°‡) increases in order < CF3). increasing consistent experimentally observed substituent effects activity. difficult to occur absence potassium phosphate (K3PO4) moderate presence K3PO4 because activates B–Ph σ-bond stabilizes dissociating B(OH)2 moiety electrostatic interaction. play an important role transmetalation; when strongly interacts Bi(diAr-SO2) species form overly stable adduct enlarge considerably ΔG°‡ value. When CH3), stabilization similar each other, destabilization more largely upon going asymmetric transition state from case than case. Thus, use favorable transmetalation. (Ph)Bi(diAr-SO2) value, whereas sulfone (SO2) replaced CH2 group. via nucleophilic attack Ph SO2. However, not most reactive only HOMO also factors such as Biδ+–(C6H3R)δ− (R = CH3 dipole moment Bi–C6H3R strength participate determining reactivity C6H3R part diArSO2. value extremely negative ΔG° Its hardly depends diAr-SO2. are key activity bismuth catalyst.

Язык: Английский

---