Probing enantioselectivity in rhodium-catalyzed Si–C bond cleavage to construct silicon-stereocenters: a theoretical study

2019 ◽  
Vol 9 (3) ◽  
pp. 646-651 ◽  
Author(s):  
Zhaoyuan Yu ◽  
Tao Zhang ◽  
Ruopeng Bai ◽  
Yu Lan
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Theoretical Study ◽  
Bond Cleavage ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Functional Theory ◽  
Elimination Process

Density functional theory (DFT) calculations indicate that favorable oxidative addition/reductive elimination process from arylrhodium complex determines the enantioselectivity.

scholarly journals Theoretical study on the mechanism of iridium-catalyzed γ-functionalization of primary alkyl C–H bonds

2016 ◽  
Vol 94 (12) ◽  
pp. 1028-1037 ◽  
Author(s):  
Zhe Li ◽  
Miaoren Xia ◽  
Russell J. Boyd
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Experimental Observation ◽  
Density Functional ◽  
Theoretical Study ◽  
Reductive Elimination ◽  
Catalytic Cycle ◽  
Catalyst Precursor ◽  
Functional Theory ◽  
Initial Formation

The mechanism of the iridium-catalyzed functionalization of a primary C–H bond at the γ position of an alcohol 5 is investigated by density functional theory (DFT) calculations. A new IrIII–IrV mechanism is found to be more feasible than the previously reported IrI–IrIII mechanism. 10 In the IrIII–IrV mechanism, the reaction begins with the initial formation of (Me4phen)IrIII(H)[Si(OR)Et2]2 from the catalyst precursor, [Ir(cod)OMe]2 (cod = 1,5-cyclooctadiene). The catalytic cycle includes five steps: (1) the insertion of norbornene into the Ir–H bond to produce (Me4phen)IrIII(norbornyl)[Si(OR)Et2]2 (R = –CH(C2H5)C3H7); (2) the Si–H oxidative addition of HSi(OR)Et2 to form (Me4phen)IrVH(norbornyl)[Si(OR)Et2]3; (3) the reductive elimination of norbornane to furnish (Me4phen)IrIII[Si(OR)Et2]3; (4) the intramolecular C–H activation of the primary C–H bond at the γ position; and (5) the Si–C reductive elimination to produce the final product and regenerate the catalyst. The highest barrier in the IrIII–IrV mechanism is 7.3 kcal/mol lower than that of the IrI–IrIII mechanism. In addition, the regioselectivity of the C–H activation predicted by this new IrIII–IrV mechanism is consistent with experimental observation.

A theoretical study of weak interactions in phenylenediamine homodimer clusters

2016 ◽  
Vol 18 (42) ◽  
pp. 29249-29257 ◽  
Author(s):  
Chengqian Yuan ◽  
Haiming Wu ◽  
Meiye Jia ◽  
Peifeng Su ◽  
Zhixun Luo ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Intermolecular Interactions ◽  
Density Functional ◽  
Theoretical Study ◽  
Natural Bond Orbital ◽  
Weak Interactions ◽  
Interaction Energies ◽  
Functional Theory ◽  
Weak Intermolecular Interactions

Utilizing dispersion-corrected density functional theory (DFT) calculations, we demonstrate the weak intermolecular interactions of phenylenediamine dimer (pdd) clusters, emphasizing the local lowest energy structures and decomposition of interaction energies by natural bond orbital (NBO) and atoms in molecule (AIM) analyses.

scholarly journals Antibacterial Activity of Amidodithiophosphonato Nickel(II) Complexes: An Experimental and Theoretical Approach

Molecules ◽  
2020 ◽  
Vol 25 (9) ◽  
pp. 2052 ◽  
Author(s):  
Enrico Podda ◽  
Massimiliano Arca ◽  
Giulia Atzeni ◽  
Simon J. Coles ◽  
Antonella Ibba ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Staphylococcus Aureus ◽  
Antimicrobial Activity ◽  
Antibacterial Activity ◽  
Dft Calculations ◽  
Density Functional ◽  
Bond Cleavage ◽  
Nickel Complexes ◽  
Functional Theory ◽  
Gram Negative

The reactions of 2,4-bis(4-methoxyphenyl)-1,3-dithio-2,4-diphosphetane-2,4-disulfide (Lawesson’s Reagent, LR) with benzylamine (BzNH2) and 4-phenylbutylamine (PhBuNH2) yield benzylammonium P-(4-methoxyphenyl)-N-benzyl-amidodithiophosphonate (BzNH3)(BzNH-adtp) and 4-phenylbutylammonium P-(4-methoxyphenyl)-N-(4-phenylbutyl)-amidodithiophosphonate (PhBuNH3)(PhBuNH-adtp). The relevant nickel complexes [Ni(BzNH-adtp)2] and [Ni(PhBuNH-adtp)2] and the corresponding hydrolysed derivatives (BzNH3)2[Ni(dtp)2] and (PhBuNH3)2[Ni(dtp)2] were prepared and fully characterized. The antimicrobial activity of the aforementioned amidodithiophosphonates against a set of Gram-positive and Gram-negative pathogen bacteria was evaluated, and [Ni(BzNH-adtp)2] and [Ni(PhBuNH-adtp)2] showed antiproliferative activity towards Staphylococcus aureus and Staphylococcus haemolyticus strains. density functional theory (DFT) calculations were performed to shed some light on the activity of reported compounds related to their tendency towards P–N bond cleavage.

Theoretical study of NHC-catalyzed C-S bond cleavage and reconstruction reaction: Mechanism, stereoselectivity, and role of catalyst

2021 ◽  
Author(s):  
Yang Wang ◽  
Yue Liu ◽  
Kaili Gong ◽  
Han Zhang ◽  
Yu Lan ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Density Functional ◽  
Theoretical Study ◽  
Bond Cleavage ◽  
Functional Theory

A theoretical study of the mechanism of the N-heterocyclic carbene (NHC)-catalyzed C-S bond cleavage and reconstruction reaction of unsaturated thioesters was conducted using density functional theory (DFT). The origin of...

Structure-activity relationships in the production of olefins from alcohols and ethers: a first-principles theoretical study

2015 ◽  
Vol 5 (9) ◽  
pp. 4547-4555 ◽  
Author(s):  
Pavlo Kostetskyy ◽  
Giannis Mpourmpakis
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Lewis Acid ◽  
First Principles ◽  
Density Functional ◽  
Theoretical Study ◽  
Functional Theory ◽  
Structure Activity Relationships ◽  
Structure Activity

Olefin formation pathways on Lewis acid (LA) sites of Al2O3, Ga2O3 and In2O3 and gallium- and indium-doped alumina were investigated using Density Functional Theory (DFT) calculations.

scholarly journals Distribution of dopant ions around poly(3,4-ethylenedioxythiophene) chains: a theoretical study

2017 ◽  
Vol 19 (15) ◽  
pp. 9889-9899 ◽  
Author(s):  
Jordi Casanovas ◽  
David Zanuy ◽  
Carlos Alemán
Keyword(s):  
Density Functional Theory ◽  
Boundary Conditions ◽  
Dft Calculations ◽  
Density Functional ◽  
Periodic Boundary ◽  
Theoretical Study ◽  
Periodic Boundary Conditions ◽  
Polymer Chains ◽  
Functional Theory

The effect of counterions and multiple polymer chains on the properties and structure of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with ClO4− has been examined using density functional theory (DFT) calculations with periodic boundary conditions (PBCs).

Oxidation of Pd(II) with Disilane in a Palladium-Catalyzed Disilylation of Aryl Halides: A Theoretical View

2021 ◽  
Author(s):  
Jing Zhang ◽  
Shihan Liu ◽  
Tao Zhang ◽  
Tao Liu ◽  
Yu Lan
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Dft Calculation ◽  
Aryl Halide ◽  
Oxidative Addition ◽  
Aryl Halides ◽  
Functional Theory ◽  
Theoretical View ◽  
Palladium Catalyzed

Density functional theory (DFT) calculation has been used to reveal the mechanism of Pd-catalyzed disilylation reaction of aryl halide. The DFT calculations indicate that the reaction starts with oxidative addition...

scholarly journals Combined the Photocatalysis and Fenton-like Reaction to Efficiently Remove Sulfadiazine in Water Using g-C3N4/Ag/γ-FeOOH: Insights Into the Degradation Pathway From Density Functional Theory

2021 ◽  
Vol 9 ◽  
Author(s):  
Yangchen Zhu ◽  
Furong Zhao ◽  
Fei Wang ◽  
Beihai Zhou ◽  
Huilun Chen ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Separation Efficiency ◽  
Bond Cleavage ◽  
Degradation Pathway ◽  
Environmental Pollutant ◽  
Functional Theory ◽  
Catalytic Material ◽  
Degradation Effect

Sulfadiazine (SDZ) is a common antibiotic pollutant in wastewater. Given that it poses a risk as an environmental pollutant, finding effective ways to treat it is important. In this paper, the composite catalytic material g-C3N4/Ag/γ-FeOOH was prepared, and its degradation performance was studied. g-C3N4/Ag/γ-FeOOH had a superior degradation effect on SDZ than g-C3N4 and γ-FeOOH. Compared with different g-C3N4 loadings and different catalyst dosages (5, 10, 25, and 50 mg/L), 2 mg/L g-C3N4/Ag/γ-FeOOH with a g-C3N4 loading of 5.0 wt% has the highest degradation promotion rate for SDZ, reaching up to 258.75% at 600 min. In addition, the photocatalytic enhancement mechanism of the catalyst was studied. Density functional theory (DFT) calculations indicated that the enhancement of photocatalytic activity was related to the narrowing of the forbidden band and the local electron density of the valence band. The bandgap of the catalyst was gradually narrowed from 2.7 to 1.05 eV, which can increase the light absorption intensity and expand the absorption edge. The density of states diagram showed that the local resonance at the interface could effectively improve the separation efficiency of e−-h+ pairs. Four degradation paths of SDZ were speculated based on DFT calculations. The analysis confirmed that the degradation path of SDZ primarily included Smiles-type rearrangement, SO2 extrusion, and S-N bond cleavage processes.

Mechanistic insight into H2-mediated Ni surface diffusion and deposition to form branched Ni nanocrystals: a theoretical study

2020 ◽  
Vol 22 (41) ◽  
pp. 23869-23877
Author(s):  
Yan Li ◽  
Ning Liu ◽  
Chengna Dai ◽  
Ruinian Xu ◽  
Bin Wu ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Ab Initio ◽  
Surface Diffusion ◽  
Density Functional ◽  
Theoretical Study ◽  
Functional Theory ◽  
Mechanistic Insight ◽  
Insight Into

Present work investigates the kinetic role of H2 during Ni surface diffusion and deposition to generate branched Ni nanostructures by employing density functional theory (DFT) calculations and ab initio molecule dynamic (AIMD) simulations.

Theoretical study on nanostructural modifications of the Si(111) surface

2019 ◽  
Vol 18 (01) ◽  
pp. 1950005
Author(s):  
Yue-Hang Dong ◽  
Xiao-Hui Liu ◽  
Wan-Sheng Su ◽  
Li-Zhen Zhao ◽  
Qing-Jun Zang ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Optical Properties ◽  
Optical Absorption ◽  
Dft Calculations ◽  
Electronic Structures ◽  
Density Functional ◽  
Theoretical Study ◽  
Surface Modifications ◽  
Thermal Stabilities ◽  
Functional Theory

Modified Si(111) surface with designed nanostructural modifications including grown pits, nanobars and nanoislands as well as deposited hill-, diamond- and cage-like nanoclusters were studied using density-functional theory (DFT) calculations. The thermal stabilities, electronic structures and optical properties of these various nanostructural modifications of the Si(111) surface were calculated and discussed. The results indicate that the optical absorption of the modified Si(111) surface can be enhanced by these surface modifications especially when depositing diamond-like nanoclusters on the surface.

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