Characterization of Iminobismuthanes and Catalytic Reduction of Organic Azides via Bi(I)/Bi(III) Redox Cycling DOI Creative Commons
Hye Won Moon,

Nils Noethling,

Markus Leutzsch

et al.

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

Published: Oct. 24, 2024

Abstract We report the stoichiometric and catalytic reactivity of organobismuth(I) complexes with organic azides. Treatment N,C,N ‐pincer bismuthinidenes azides (acyl, sulfonyl, bulky aryl) results in monomeric iminobismuthanes which can be structurally characterized —including formal Bi=N double bond— by multinuclear NMR spectroscopy single‐crystal X‐ray diffraction. Building upon iminobismuthanes, reduction a broad range is developed. DFT calculations reaction pathway support redox nature overall process.

Language: Английский

Bi-Catalyzed Trifluoromethylation of C(sp2)–H Bonds under Light DOI Creative Commons
Takuya Tsuruta, Davide Spinnato, Hye Won Moon

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(47), P. 25538 - 25544

Published: Nov. 14, 2023

We disclose a Bi-catalyzed C–H trifluoromethylation of (hetero)arenes using CF3SO2Cl under light irradiation. The catalytic method permits the direct functionalization various heterocycles bearing distinct functional groups. structural and computational studies suggest that process occurs through an open-shell redox manifold at bismuth, comprising three unusual elementary steps for main group element. cycle starts with rapid oxidative addition to low-valent Bi(I) catalyst, followed by light-induced homolysis Bi(III)–O bond generate trifluoromethyl radical upon extrusion SO2, is closed hydrogen-atom transfer Bi(II) intermediate.

Language: Английский

Citations

35
Bismuth in Radical Chemistry and Catalysis DOI Creative Commons
Mauro Mato, Josep Cornellà

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(8)

Published: Nov. 22, 2023

Abstract Whereas indications of radical reactivity in bismuth compounds can be traced back to the 19 th century, preparation and characterization both transient persistent bismuth‐radical species has only been established recent decades. These advancements led emergence field chemistry, mirroring progress seen for other main‐group elements. The seminal fundamental studies this area have ultimately paved way development catalytic methodologies involving intermediates, a promising approach that remains largely untapped broad landscape synthetic organic chemistry. In review, we delve into milestones eventually present state‐of‐the‐art Our focus aims at outlining intrinsic discoveries inorganic/organometallic chemistry contextualizing their practical applications synthesis catalysis.

Language: Английский

Citations

32
Theoretical Study on Bismuth(III) Catalysts for Synthesis of Phenylsulfonyl Fluoride: Reasons of Their Catalysis DOI
Yu Tian, Shigeyoshi Sakaki

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2758 - 2774

Published: Feb. 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.

Language: Английский

Citations

3
NCN-pincer organopnictogen(iii) bis(aryloxides) DOI
Gabriel Duneş, Cristian Silvestru

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(12), P. 5523 - 5529

Published: Jan. 1, 2024

New hypercoordinated organopnictogen( iii ) bis(aryloxides), ArPn(SC 6 H 3 R 2 -2,6) (Pn = Sb, Bi; Ar NCN-pincer ligand; i Pr, OMe), have been prepared and their solution solid state structures investigated.

Language: Английский

Citations

3
Activation and Catalytic Degradation of SF6 and PhSF5 at a Bismuth Center DOI Creative Commons
Vanessa A. Béland,

Nils Nöthling,

Markus Leutzsch

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25409 - 25415

Published: Sept. 3, 2024

In this work, we report the catalytic degradation of SF

Language: Английский

Citations

3
Hydrobismuthation: Insertion of Unsaturated Hydrocarbons into the Heaviest Main Group Element Bond to Hydrogen DOI Creative Commons
Kristian L. Mears,

Gia-Ann Nguyen,

Bronson Ruiz

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(1), P. 19 - 23

Published: Jan. 2, 2024

The bismuth hydride (2,6-Mes2H3C6)2BiH (1, Mes = 2,4,6-trimethylphenyl), which has a Bi–H 1H NMR spectroscopic signal at δ 19.64 ppm, was reacted with phenylacetylene 60 °C in toluene to yield [(2,6-Mes2C6H3)2BiC(Ph)=CH2] (2) after 15 min. Compound 2 characterized by 1H, 13C NMR, and UV–vis spectroscopy, single crystal X-ray crystallography, calculations employing density functional theory. is the first example of hydrobismuthation addition product displays Markovnikov regioselectivity. Computational methods indicated that it forms via radical mechanism an associated Gibbs energy activation 91 kJ mol–1 reaction −90 mol–1.

Language: Английский

Citations

2
Synthesis of bismuthanyl-substituted monomeric triel hydrides DOI Creative Commons

Robert Szlosek,

Christian Marquardt,

Oliver Hegen

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14837 - 14843

Published: Jan. 1, 2024

The syntheses of first, extremely sensitive donor-stabilized monomeric bismuthanylboranes D·BH 2 Bi(SiMe 3 ) (D = NHC, DMAP) and the bismuthanylgallane IDipp·GaH are presented representing unique element combinations bismuth triels.

Language: Английский

Citations

2
Bismuth in Radical Chemistry and Catalysis DOI Creative Commons
Mauro Mato, Josep Cornellà

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(8)

Published: Nov. 22, 2023

Abstract Whereas indications of radical reactivity in bismuth compounds can be traced back to the 19 th century, preparation and characterization both transient persistent bismuth‐radical species has only been established recent decades. These advancements led emergence field chemistry, mirroring progress seen for other main‐group elements. The seminal fundamental studies this area have ultimately paved way development catalytic methodologies involving intermediates, a promising approach that remains largely untapped broad landscape synthetic organic chemistry. In review, we delve into milestones eventually present state‐of‐the‐art Our focus aims at outlining intrinsic discoveries inorganic/organometallic chemistry contextualizing their practical applications synthesis catalysis.

Language: Английский

Citations

3
C–H bond activation at antimony(iii): synthesis and reactivity of Sb(iii)–oxyaryl species DOI Creative Commons

Gabriel Duneş,

Marie Cordier≈, Samia Kahlal

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

We report on the synthesis, structure and reactivity of [{NCN

Language: Английский

Citations

0
Characterization of Iminobismuthanes and Catalytic Reduction of Organic Azides via Bi(I)/Bi(III) Redox Cycling DOI Creative Commons
Hye Won Moon,

Nils Noethling,

Markus Leutzsch

et al.

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

Published: Oct. 24, 2024

Abstract We report the stoichiometric and catalytic reactivity of organobismuth(I) complexes with organic azides. Treatment N,C,N ‐pincer bismuthinidenes azides (acyl, sulfonyl, bulky aryl) results in monomeric iminobismuthanes which can be structurally characterized —including formal Bi=N double bond— by multinuclear NMR spectroscopy single‐crystal X‐ray diffraction. Building upon iminobismuthanes, reduction a broad range is developed. DFT calculations reaction pathway support redox nature overall process.

Language: Английский

Citations

0