BONDING FEATURES AND REACTION MECHANISM OF THE OXIDATION OF 2-PROPANOL BY A Cp*Ir AMIDO COMPLEX

2010 ◽  
Vol 09 (supp01) ◽  
pp. 99-107
Author(s):  
LINGJUN LIU ◽  
SIWEI BI ◽  
MIN SUN ◽  
XIANGAI YUAN ◽  
PING LI
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Dft Calculations ◽  
Density Functional ◽  
Bond Distance ◽  
Mechanistic Study ◽  
Functional Theory ◽  
Rate Determining Step ◽  
Model Complex ◽  
Membered Transition State

The mechanistic study on the oxidation of 2-propanol by the model complex CpIr [κ2-(N,C)-( NHCMe2–2-C6H4)] (R) is performed using density functional theory (DFT) calculations. It is found that the rate-determining step is the hydrogen migration from 2-propanol to R via a six-membered transition state. The reaction is calculated to be favorable thermodynamically. To further understand the reaction mechanism, some bonding features are discussed, such as the correlation of the geometry of R and the Ir–N π bond involved, the transformation of the nitrogen hybridization, the variation of Ir–N bond distance, and so on.

Catalytic polymerization of naphthalene by HF/BF3 super acid: an ab initio density functional theory study

2018 ◽  
Vol 20 (36) ◽  
pp. 23311-23319 ◽  
Author(s):  
Po-Yu Yang ◽  
Hsing-Yin Chen ◽  
Shin-Pon Ju ◽  
Chia-Lin Chang ◽  
Gao-Shee Leu ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Dft Calculations ◽  
Ab Initio ◽  
Density Functional ◽  
Catalytic Polymerization ◽  
Density Functional Theory Study ◽  
Functional Theory ◽  
Detailed Reaction Mechanism ◽  
Super Acid

The detailed reaction mechanism of naphthalene catalytic polymerization by HF/BF3 has been investigated by DFT calculations and the directionality of the naphthalene-derived mesophase molecule has been explained.

Oxygen reduction reaction mechanism on P, N co-doped graphene: a density functional theory study

2019 ◽  
Vol 43 (48) ◽  
pp. 19308-19317 ◽  
Author(s):  
Zhao Liang ◽  
Chao Liu ◽  
Mingwei Chen ◽  
Xiaopeng Qi ◽  
Pramod Kumar U. ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Catalytic Activity ◽  
Reaction Mechanism ◽  
Dft Calculations ◽  
Density Functional ◽  
Reduction Reaction ◽  
Density Functional Theory Study ◽  
Functional Theory ◽  
Doped Graphene ◽  
Co Doped

DFT calculations confirmed that the P–N coupled site changed the ORR pathway and improved the catalytic activity compared with single doping.

scholarly journals Synthesis of Pyrroles Through the CuH-Catalyzed Coupling of Enynes and Nitriles

2020 ◽  
Author(s):  
Yujing Zhou ◽  
Lin Zhou ◽  
Luke T. Jesikiewicz ◽  
Peng Liu ◽  
Stephen L. Buchwald
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Dft Calculations ◽  
Efficient Method ◽  
Density Functional ◽  
Coupling Reaction ◽  
Copper Hydride ◽  
Reductive Coupling ◽  
Functional Theory ◽  
Subsequent Cyclization

<p>Herein, we describe an efficient method to prepare polysubstituted pyrroles via a copper-hydride (CuH)-catalyzed enyne-nitrile coupling reaction. This protocol accommodates both aromatic and aliphatic substituents and a broad range of functional groups, providing a variety of N-H pyrroles in good yields and with high regioselectivity. We propose that the Cu-based catalyst promotes both the initial reductive coupling and subsequent cyclization steps. Density functional theory (DFT) calculations were performed to elucidate the reaction mechanism.</p>

Theoretical studies on the mechanism of Ru(ii)-catalyzed regioselective C–H allylation of indoles with allyl alcohols

2019 ◽  
Vol 48 (25) ◽  
pp. 9181-9186 ◽  
Author(s):  
Chao Deng ◽  
Po Hu ◽  
YouJia Wang ◽  
Shaowei Wang ◽  
Weihua Zhang
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Dft Calculations ◽  
Density Functional ◽  
Theoretical Studies ◽  
Functional Theory ◽  
Allyl Alcohols

The reaction mechanism of the Ru(ii)-catalyzed regioselective C–H allylation of indoles with allyl alcohols has been studied by density functional theory (DFT) calculations.

Computational study on gold-catalyzed (4 + 3) intramolecular cycloaddition of trienyne: mechanism, reactivity and selectivity

RSC Advances ◽  
2016 ◽  
Vol 6 (77) ◽  
pp. 73454-73468 ◽  
Author(s):  
Meng-Ru Li ◽  
Gui-Chang Wang
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Dft Calculations ◽  
Density Functional ◽  
Computational Study ◽  
Functional Theory ◽  
Intramolecular Cycloaddition

The reaction mechanism, reactivity and selectivity of the Au(i)-catalyzed intramolecular (4 + 3) cycloaddition of trienyne have been studied by density functional theory (DFT) calculations.

Mechanistic Study of the Cooperative Palladium/Lewis Acid-Catalyzed Transfer Hydrocyanation Reaction: The Origin of the Regioselectivity

2021 ◽  
Author(s):  
Dandan Jiang ◽  
Xiaojun Li ◽  
Jiali Cai ◽  
Yuna Bai ◽  
Lixiong Zhang ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Lewis Acid ◽  
Density Functional ◽  
Catalytic Mechanism ◽  
Mechanistic Study ◽  
Functional Theory ◽  
Terminal Alkenes ◽  
Acid Catalyzed ◽  
Insight Into

Density functional theory (DFT) calculations have been performed to gain insight into the catalytic mechanism of the Palladium/Lewis acid-catalyzed transfer hydrocyanation of terminal alkenes to reach the linear alkyl nitrile...

Hydrogenation of CO2 to Methanol Catalyzed by Manganese Pincer Complex: Insights on Mechanism and Solvent Effect

2021 ◽  
Author(s):  
Lin Zhang ◽  
Min Pu ◽  
Ming Lei
Keyword(s):  
Carbon Dioxide ◽  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Dft Calculations ◽  
Solvent Effect ◽  
Density Functional ◽  
Functional Theory ◽  
Hydrogenation Of Co2 ◽  
Pincer Complex ◽  
Hydrogenation Of Carbon Dioxide

Herein density functional theory (DFT) calculations were employed to explore the reaction mechanism of three cascade cycles for the hydrogenation of carbon dioxide to methanol (CO2 + 3H2 → CH3OH...

scholarly journals Combustion behaviors of hydrogenated and unhydrogenated colophony esters/petroleum resins using TG-FTIR and DFT analysis

2021 ◽  
Author(s):  
Dan Zhou ◽  
Xiaopeng Chen ◽  
Jiezhen Liang ◽  
Xiaojie Wei ◽  
Chenghong Wu ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Dft Calculations ◽  
Carbonyl Compounds ◽  
Density Functional ◽  
Functional Theory ◽  
Master Plots ◽  
Glycerol Ester ◽  
Friedman Method ◽  
Combustion Behaviors

The combustion behavior of tackifying resins (such as glycerol ester of colophony/hydrogenated colophony and C9/hydrogenated C9 petroleum resin, namely GEC, GEHC, C9PR and HC9PR, respectively) were investigated using TG-FTIR and density functional theory (DFT) analyses. Results from combustion characteristics indicate tackifying resins and their wastes are a promising fuel for generating energy. The average activation energies obtained by Friedman method for GEC, GEHC, C9PR and HC9PR were 223.51, 162.16, 166.52 and 116.20 kJ/mol, respectively, revealing that (H)C9PR were more readily combustible than GE(H)C, and their hydrogenated products burned more easily than their unhydrogenated ones, which were strongly supported by the TG-FTIR results. DFT calculations also show that the bond dissociation energy of C-C bond of GEC is higher than those of C9PR and GEHC. The best appropriate reaction mechanism evaluated by integral master plots is f(α)=3(1-α)2/3. Volatiles are mainly composed of H2O, CH4, CO2, CO, alcohol, aromatic and carbonyl compounds.

scholarly journals Theoretical investigation on the effect of the ligand on bis-silylation of C(sp)–C(sp) by Ni complexes

RSC Advances ◽  
2022 ◽  
Vol 12 (2) ◽  
pp. 1005-1010
Author(s):  
Li Hui ◽  
He Yuhan ◽  
Wang Jiaqi
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Transition Metal ◽  
Theoretical Investigation ◽  
Density Functional ◽  
Active Catalyst ◽  
Organic Ligand ◽  
Organic Complex ◽  
Functional Theory ◽  
Rate Determining Step

Density functional theory (DFT) is used to study the bis-silylation of alkynes catalyzed by a transition metal nickel–organic complex; the active catalyst, the organic ligand, the reaction mechanism, and rate-determining step are discussed in this paper.

Zur Elektronenstruktur metallorganischer Komplexe der ƒ -Elemente, 81. Berechnung der Normalschwingungen von La(η5-C5H5)3(NCCH3)2 auf der Basis der Dichtefunktionaltheorie sowie vibronische Kopplungen und Auffindung weiterer rein elektronischer Absorptions- und Lumineszenzüberg¨ange bei [La(η5-C5H5)3(NCCH3)2:Nd3+] / Electronic Structures of Organometallic Complexes of f Elements, 81. Calculation of the Normal Modes of La(η5-C5H5)3(NCCH3)2 on the Basis of Density Functional Theory as well as Vibronic Couplings and Identification of Further Purely Electronic Absorption and Luminescence Transitions of [La(η5-C5H5)3(NCCH3)2:Nd3+]

2013 ◽  
Vol 68 (12) ◽  
pp. 1356-1370 ◽  
Author(s):  
Hanns-Dieter Amberger ◽  
Hauke Reddmann
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Normal Modes ◽  
Organometallic Complexes ◽  
Functional Theory ◽  
Model Calculations ◽  
Model Complex ◽  
Electronic Crystal ◽  
Vibronic Couplings

The planned model calculations of normal modes of pseudo-trigonal-bipyramidal LaCp3(NCCH3)2 (Cp = η5-C5H5-) (1) adopting density functional theory (DFT), and using the molecular structure as suggested by X-ray investigations, did not converge. Alternatively, DFT calculations assuming molecular C3h symmetry were performed. Unfortunately, these calculations did not reproduce the experimentally derived frequencies of the skeletal modes very well, including a wrong energetic sequence of the four previously unambiguously assigned (close lying) Raman-active ν(La-Cp) skeletal modes. The same presumably also holds for DFT calculations made for LaCp3 · NCCH3 (2) and base-free LaCp3 (3), assuming molecular C3 and C3h symmetry, respectively. In order to check whether the calculated incorrect sequence is produced by the five-membered Cp rings, a DFT calculation also has been performed for the hypothetical model complex [La(η6-C6H6)3]3+ (4) of D3 symmetry. A closer examination of the vibronic sidebands of the hypersensitive absorption transition 4I9/2 → 4G5/2 of [LaCp3(NCCH3)2:Nd3+] (5) showed that first of all, totally symmetric intraligand and not skeletal vibrations are coupling as it was the case for [LaCp3(NCCH3)2:Ln3+] (Ln = Pr, Sm). Applying this result to the vibronic sidebands of some purely electronic crystal field (CF) transitions, which are hampered by strong binary combination vibrations, the energies of these CF levels could be determined. The CF state 1Γ8 of the ground multiplet 4I9/2 of [LaCp3(NCCH3)2:Nd3+], which previously could not be detected by absorption measurements, could be derived from the luminescence transition 4F3/2 → 4I9/2. Considering these additional assignments, the goodness of the fit increased from 32.3 to 29.9 cm-1 for 61 assignments

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