Photoinduced Mechanisms of C–S Borylation of Methyl(p-tolyl)Sulfane with Bis(Pinacolato)diboron: A Density Functional Theory Investigation DOI Open Access

Yuxiao Ming,

Tiantian Feng,

Bin Chen

et al.

Catalysts, Journal Year: 2024, Volume and Issue: 14(8), P. 550 - 550

Published: Aug. 22, 2024

The reaction mechanisms of C–S borylation aryl sulfides catalyzed with 1,4-benzoquinone (BQ) were investigated by employing the M06-2X-D3/ma-def2-SVP method and basis set. In this study, SMD model was taken to simulate solvent effect 1,4-dioxane. Also, TD-DFT calculations BQ methyl(p-tolyl)sulfane performed in an model. computational results indicated that methyl(p-tolyl)sulfane, serving as a photo-catalyst, would be excited under blue LED 450 nm, aligning well experimental observations. Additionally, role 3O2 investigated, revealing it could activated into 1O2 from released energy 1[BQ + methyl(p-tolyl)sulfane]* or 3[BQ methyl(p-tolyl)sulfane]*→BQ process. Then, 1O2, bis(pinacolato)diboron, would, through series reactions, yield final product, P. Gibbs free surface shows path a2-2 is optimal, has fewer steps lower barrier. Electron spin density isosurface graphs employed analyze structures elucidate single electron distribution. These offer valuable insights studied interactions related processes shed light on governing b2pin2 methyl(p-tolyl)sulfane.

Language: Английский

Mechanisms of C(sp3)-H Functionalization of Acetonitrile or Acetone with Alkynes: A DFT Investigation DOI
Bin Chen,

Tiantian Feng,

Da‐Gang Zhou

et al.

Journal of Chemical Information and Modeling, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

The mechanisms for the C(sp3)-H activation and addition reactions between acetonitrile (or acetone) alkynes have been investigated with M06-2X-D3/ma-def2-TZVP method basis set. SMD (solvation model based on solute electron density) was applied to simulate solvent effect. In first second reactions, 2-phenylbut-3-yn-2-ol reacted acetone, respectively. First, activations of acetone could be achieved by PhCOO• t-BuO• radicals. Then, converted into final products P1 P2. Gibbs free energy surfaces these two suggest that blue lines would favorable paths lower barriers, terminal C atom C≡C bond is best reactive site. Moreover, analysis IRI (Interaction Region Indicator) reveals Z- E-configuration transformations. While in third fourth methyl(2-(phenylethynyl)phenyl)sulfane has interactions via some paths, profiles show C10 atom, rather than C11 priority, are favorable. Furthermore, action mode Na2HPO4 reduce barrier benefit reaction. vdW (van der Waals) play an important role choice fifth sixth) reaction, it happened 1-(2-(methylthio)phenyl)-3-phenylprop-2-yn-1-one acetontrile yield product P5 P6). computational results uncovered line path, site depends interactions, which origin selectivity. addition, investigation byproducts carried out, can explain reason only main produced. Both those agree experimental results. localized orbital locator (LOL) isosurfaces, Laplacian order (LBO), density critical point (ρBCP), spin isosurface graphs, graphs used analyze structure reveal reaction substances.

Language: Английский

Citations

0
Mechanism of C H alkylation of cyclic sulfonamides and Cyclohexylboronic acid: A DFT investigation DOI
Yuhan Shi, Da‐Gang Zhou

Computational and Theoretical Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 115220 - 115220

Published: April 1, 2025

Language: Английский

Citations

0
Efficient Electrophotochemical Microreactor for Direct Green Production of Phenol from Benzene DOI
Zhiming Ding, Danfeng Wang, Gang Wang

et al.

Industrial & Engineering Chemistry Research, Journal Year: 2025, Volume and Issue: unknown

Published: April 30, 2025

Language: Английский

Citations

0
Alkali Metal-Hydroxide-Catalyzed Mechanisms of Csp-H Silylation of Alkyne: A DFT Investigation DOI

Tiantian Feng,

Ying Lin,

Bin Chen

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(31), P. 6352 - 6361

Published: Jan. 1, 2024

MOH/MH-catalytic mechanisms for Csp–H silylation were investigated using DFT.

Language: Английский

Citations

3
Photoinduced Mechanisms of C–S Borylation of Methyl(p-tolyl)Sulfane with Bis(Pinacolato)diboron: A Density Functional Theory Investigation DOI Open Access

Yuxiao Ming,

Tiantian Feng,

Bin Chen

et al.

Catalysts, Journal Year: 2024, Volume and Issue: 14(8), P. 550 - 550

Published: Aug. 22, 2024

The reaction mechanisms of C–S borylation aryl sulfides catalyzed with 1,4-benzoquinone (BQ) were investigated by employing the M06-2X-D3/ma-def2-SVP method and basis set. In this study, SMD model was taken to simulate solvent effect 1,4-dioxane. Also, TD-DFT calculations BQ methyl(p-tolyl)sulfane performed in an model. computational results indicated that methyl(p-tolyl)sulfane, serving as a photo-catalyst, would be excited under blue LED 450 nm, aligning well experimental observations. Additionally, role 3O2 investigated, revealing it could activated into 1O2 from released energy 1[BQ + methyl(p-tolyl)sulfane]* or 3[BQ methyl(p-tolyl)sulfane]*→BQ process. Then, 1O2, bis(pinacolato)diboron, would, through series reactions, yield final product, P. Gibbs free surface shows path a2-2 is optimal, has fewer steps lower barrier. Electron spin density isosurface graphs employed analyze structures elucidate single electron distribution. These offer valuable insights studied interactions related processes shed light on governing b2pin2 methyl(p-tolyl)sulfane.

Language: Английский

Citations

0