Computational and Theoretical Chemistry最新文献_第2页

The role of amylose and amylopectin in selective flocculation of iron ore slimes 直链淀粉和支链淀粉在铁矿泥选择性絮凝中的作用

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-07-19 DOI: 10.1016/j.comptc.2025.115360

Maryam Khosravi, Sima Mohammadnejad

{"title":"The role of amylose and amylopectin in selective flocculation of iron ore slimes","authors":"Maryam Khosravi, Sima Mohammadnejad","doi":"10.1016/j.comptc.2025.115360","DOIUrl":"10.1016/j.comptc.2025.115360","url":null,"abstract":"<div><div>With the depletion of high-grade iron ore reserves, starch-based selective flocculation has proven to be an effective technique for processing ultrafine iron ore particles. Here, molecular modelling has been employed to examine the adsorption mechanism of starch polymer components, amylose and amylopectin, on hematite and goethite as well as gangue minerals of quartz and kaolinite. Through the DFT method, this research clarifies the contribution of amylose and amylopectin to the flocculation selectivity of starch by adsorbed polymer geometry as well as adsorption energies on the surfaces of each mineral. The obtained results illustrates that the amount of absorption energy of amylose on both hematite and gangue minerals is higher than that of amylopectin, and the amount of absorption energy obtained for both amylose and amylopectin in the case of hematite and goethite is significantly higher than that of quartz and kaolinite (Al-OH end). The results suggest that both amylopectin and amylose play the role in the selectivity of flocculants, which contrasts with earlier studies that attributed the selectivity of starch solely to amylose. The Fe<img>O chemical bond acts as the primary interaction mechanism linking the starch components with both hematite and goethite, while a considerably weaker hydrogen bond supports the interaction between kaolinite and amylose.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115360"},"PeriodicalIF":3.0,"publicationDate":"2025-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144686013","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Chalcones from the deep: in silico medicinal chemistry and quantum chemical insights into their anticancer and anti-HIV potency 深查尔酮：在硅药物化学和量子化学洞察其抗癌和抗艾滋病毒效力

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-07-18 DOI: 10.1016/j.comptc.2025.115380

Saeedah Musaed Almutairi , Rabbia Mehmood , Arooj Fatima , Danish Ali , Maryum Jamal , Muhammad Ayyaz , Muhammad Sarfraz

{"title":"Chalcones from the deep: in silico medicinal chemistry and quantum chemical insights into their anticancer and anti-HIV potency","authors":"Saeedah Musaed Almutairi , Rabbia Mehmood , Arooj Fatima , Danish Ali , Maryum Jamal , Muhammad Ayyaz , Muhammad Sarfraz","doi":"10.1016/j.comptc.2025.115380","DOIUrl":"10.1016/j.comptc.2025.115380","url":null,"abstract":"<div><div>Chalcones obtained from marine sources have become significant frameworks in the discovery of potential innovative therapies. This work thoroughly explored a library of over 100 chalcones for their dual anticancer and anti-HIV potential using combined quantum chemistry and molecular modeling methodologies. DFT simulations at the B3LYP-D3/6-31+G(d) level included HOMO–LUMO, DOS, ESP mapping, and NBO. Molecular docking conducted against two targets, epidermal growth factor receptor (EGFR, PDB ID: <span><span>1NQL</span><svg><path></path></svg></span>) and HIV-II protease (PDB ID: <span><span>1HSG</span><svg><path></path></svg></span>), revealed the significance of chalcones (<strong>C-1</strong>, <strong>C-3</strong>, <strong>C-6</strong>, and <strong>C-9</strong>), confirming robust binding affinities (up to −9.48 kcal/mol). MD simulations confirmed the structural integrity of the ligand-protein complexes. To substantiate the computational methods, DFT-derived NMR and IR spectra of an analogue of <strong>C-6</strong> (phlorizin) were compared with experimental data, demonstrating remarkable concordance and affirming the theoretical framework. The results underscore the potential of marine chalcones as dual-action therapeutic agents for cancer and HIV therapy.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115380"},"PeriodicalIF":3.0,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144686125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Solid-state fluorescence modulation and DFT analysis of charge-transfer cocrystal of anthracene-chalcone-pyridine compounds 蒽-查尔酮-吡啶类化合物电荷转移共晶的固态荧光调制和DFT分析

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-07-15 DOI: 10.1016/j.comptc.2025.115377

Xianliang Gong , Yue Zhang , Zhouyu Jiang , Cunbin Du , Arshad Khan , Rabia Usman

{"title":"Solid-state fluorescence modulation and DFT analysis of charge-transfer cocrystal of anthracene-chalcone-pyridine compounds","authors":"Xianliang Gong , Yue Zhang , Zhouyu Jiang , Cunbin Du , Arshad Khan , Rabia Usman","doi":"10.1016/j.comptc.2025.115377","DOIUrl":"10.1016/j.comptc.2025.115377","url":null,"abstract":"<div><div>Charge transfer (CT) cocrystals formed via non-covalent interactions play a pivotal role in governing their optical behaviors. A CT cocrystals were synthesized using 1,2,4,5-tetracyanobenzene (TCNB) as the electron acceptor and chalcone (E)-3-(anthracen-9-yl)-1-(pyridin-3-yl)prop-2-en-1-one (A3BPO) as the electron donor. Structural analysis through single-crystal X-ray diffraction (SC-XRD) unveiled that this cocrystal predominantly comprise a mixed stacking arrangement guided by face-to-face π···π interactions, with the overall stability of CT cocrystal stacking bolstered by auxiliary hydrogen bonds. The relationship between structure and properties was scrutinized using various analytical techniques including Powder X-ray diffraction (PXRD), FT-IR, UV–visible absorption, and fluorescence spectroscopy. Density functional theory (DFT) simulations elucidated that the modified optical properties primarily stem from CT between acceptor and donor. These findings contribute significantly to a clearer understanding of how stacking modes in CT cocrystals influence the interplay between CT and optical properties.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115377"},"PeriodicalIF":3.0,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144655556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Molecular engineering of novel push-pull biphenylene bridge chromophores for achieving remarkable nonlinear optical properties and tuning aromaticity 新型推挽式联苯桥式发色团的分子工程，以实现卓越的非线性光学性质和芳香性调谐

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-07-14 DOI: 10.1016/j.comptc.2025.115372

Hejing Sun

{"title":"Molecular engineering of novel push-pull biphenylene bridge chromophores for achieving remarkable nonlinear optical properties and tuning aromaticity","authors":"Hejing Sun","doi":"10.1016/j.comptc.2025.115372","DOIUrl":"10.1016/j.comptc.2025.115372","url":null,"abstract":"<div><div>A series of novel biphenylene (BPE) bridge chromophores possessing powerful push-pull effect, unique aromaticity and excited-state features has been designed and systematically investigated for the first time. Utilizing the multiple advanced methods, this study has successfully revealed the relationship between (anti)aromaticity, push-pull effects, excited-state characteristics, and nonlinear optical (NLO) properties of new BPE chromophores. The unique BPE-bridged chromophores have double-stranded conjugated framework, more π-electrons and broader conjugation pathways compared to the currently popular NLO conjugated bridges. Notably, by modulating the number and arrangement of fused (anti)aromatic rings within the BPE-conjugated bridge, the electronic structure, aromaticity, excited-state properties, charge transfer processes, and NLO activities of BPE chromophores are effectively tuned. Excitingly, compared to the representative chromophores, the DN-BPE5-AS and DN-BPE3-AS both have the remarkable β<sub>prj</sub> values of 2229.7 ✕10<sup>−30</sup> and 2184.5✕10<sup>−30</sup> esu in CHCl<sub>3</sub>, respectively. Significantly, it was found that the crucial state determining NLO activities in the novel BPE chromophore can vary due to the its diverse (anti)aromaticity and electronic structure. All BPE chromophores displayed excellent electro-optical Pockels and optical rectification effects. The outstanding NLO performance and unique structure of new BPE chromophores make them promising for applications in chip-scale optoelectronic integrated circuits, driving advancements in logic and digital technologies</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115372"},"PeriodicalIF":3.0,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144623265","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Potential application of BC2N monolayer as an anode for K-ion batteries: A theoretical study BC2N单层作为k离子电池负极的潜在应用：理论研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-07-14 DOI: 10.1016/j.comptc.2025.115374

Maryam Hussein Abdulameer , Ammar Kh. Hammad , Ibrahm Mahariq , Prakash Kanjariya , Asha Rajiv , Aman Shankhyan , Helen Merina Albert , Mehul Manu , M. Shakir , Hamad M. Alkahtani

{"title":"Potential application of BC2N monolayer as an anode for K-ion batteries: A theoretical study","authors":"Maryam Hussein Abdulameer , Ammar Kh. Hammad , Ibrahm Mahariq , Prakash Kanjariya , Asha Rajiv , Aman Shankhyan , Helen Merina Albert , Mehul Manu , M. Shakir , Hamad M. Alkahtani","doi":"10.1016/j.comptc.2025.115374","DOIUrl":"10.1016/j.comptc.2025.115374","url":null,"abstract":"<div><div>Density functional theory based on the B3LYP-gCP-D3 model was used to investigate the BC2N nanosheet (BC<sup>2</sup>NNS) as an anode material in K ion batteries (KIBs). Two types of nonaromatic hexagonal rings were identified: B<sup>2</sup>C<sup>2</sup>N<sup>2</sup> (I) and BC<sup>4</sup>N (II). The K cation adheres to B<sup>2</sup>C<sup>2</sup>N<sup>2</sup> via cation-lone-pair interaction with an adhesion energy of −43.5 kcal/mol, while it interacts with BC4N through cation-<em>π</em> interaction, with an energy of −40.4 kcal/mol. The adhesion energy for K is −6.6 kcal/mol, with a significant dispersion term of −5.2 kcal/mol. The structure of BC<sup>2</sup>NNS remains stable during K/K<sup>+</sup> adsorption, requiring a maximum energy barrier of 14.1 kcal/mol for migration, leading to a diffusion coefficient of 1.07 × 10–11 cm<sup>2</sup>/s. The cell voltage is 1.60 V, indicating BC<sup>2</sup>NNS's potential as an anode material for KIBs.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115374"},"PeriodicalIF":3.0,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144663302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Investigation of electronic and nonlinear optical properties of two-unit BODIPY systems linked by π-bridges using advanced Python-based analysis tools 利用先进的python分析工具研究π桥连接的双单元BODIPY系统的电子和非线性光学性质

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-07-12 DOI: 10.1016/j.comptc.2025.115375

Kamal Ziadi

{"title":"Investigation of electronic and nonlinear optical properties of two-unit BODIPY systems linked by π-bridges using advanced Python-based analysis tools","authors":"Kamal Ziadi","doi":"10.1016/j.comptc.2025.115375","DOIUrl":"10.1016/j.comptc.2025.115375","url":null,"abstract":"<div><div>This study explores the electronic and second-order nonlinear optical (NLO) properties of cyclic and linear BODIPY-based chromophores, aiming to identify structural features that enhance hyperpolarizability (β). Using DFT and TD-DFT, alongside a custom Python tool (<span><span>K.Z.py</span><svg><path></path></svg></span>) for data visualization and analysis, we evaluated charge-transfer pathways, electronic transitions, and NLO responses at wavelengths of 1064 nm and 1907 nm. Our results show that linear configurations with thiophene-based π-bridges (notably L5 and L6) exhibit significantly higher hyperpolarizabilities, up to 2.50 × 10<sup>5</sup> a.u., compared to cyclic analogues, due to improved planarity and conjugation. DOS and PDOS analyses revealed how BODIPY cores and π-bridges contribute to the electronic structure and charge delocalization that drive NLO behavior. Unit Sphere Representation (USR) and harmonic light intensity analyses further confirmed dominant octupolar responses in these molecules. These findings provide valuable insights for the rational design of high-performance NLO materials for optoelectronic applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115375"},"PeriodicalIF":3.0,"publicationDate":"2025-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144632854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Schrödinger equation with Pauli–Fierz Hamiltonian and double well potential as model of vibrationally enhanced tunneling for proton transfer in hydrogen bond Schrödinger用Pauli-Fierz哈密顿量和双阱势作为氢键中质子转移振动增强隧道模型的方程

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-07-11 DOI: 10.1016/j.comptc.2025.115320

A.E. Sitnitsky

{"title":"Schrödinger equation with Pauli–Fierz Hamiltonian and double well potential as model of vibrationally enhanced tunneling for proton transfer in hydrogen bond","authors":"A.E. Sitnitsky","doi":"10.1016/j.comptc.2025.115320","DOIUrl":"10.1016/j.comptc.2025.115320","url":null,"abstract":"<div><div>A solution of the two-dimensional Schrödinger equation with Pauli–Fierz Hamiltonian and trigonometric double-well potential is obtained within the framework of the first-order of adiabatic approximation. The case of vibrational strong coupling is considered which is pertinent for polariton chemistry and (presumably) for enzymatic hydrogen transfer. We exemplify the application of the solution by calculating the proton transfer rate constant in the hydrogen bond of the Zundel ion H<sub>5</sub>O<sub>2</sub><sup>+</sup> (oxonium hydrate) within the framework of the Weiner’s theory. An analytic formula is derived which provides the calculation of the proton transfer rate with the help of elements implemented in <em>Mathematica</em>. The parameters of the model for the Zundel ion are extracted from the literature data on IR spectroscopy and quantum chemical calculations. The approach yields a vivid manifestation of the phenomenon of vibrationally enhanced tunneling, i.e., a sharp bell-shaped peak of the rate enhancement by the external vibration at its symmetric coupling to the proton coordinate. The results obtained testify that the effect of resonant activation in our model is robust and stable to variations in the types of the quadratically coupled mode (vibrational strong coupling or symmetric one).</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115320"},"PeriodicalIF":3.0,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Thermodynamic and quantum chemistry calculations of species in the molten AlCl3–MCl (M = Li, Na, K) system 熔融AlCl3-MCl （M = Li, Na， K）体系中物质的热力学和量子化学计算

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-07-08 DOI: 10.1016/j.comptc.2025.115368

Ruidong Guo , Xianwei Hu , Liang Tian , Hongguang Kang , Ao Xu , Zhongning Shi , Zhaowen Wang

{"title":"Thermodynamic and quantum chemistry calculations of species in the molten AlCl3–MCl (M = Li, Na, K) system","authors":"Ruidong Guo , Xianwei Hu , Liang Tian , Hongguang Kang , Ao Xu , Zhongning Shi , Zhaowen Wang","doi":"10.1016/j.comptc.2025.115368","DOIUrl":"10.1016/j.comptc.2025.115368","url":null,"abstract":"<div><div>The Hall–Héroult process dominates aluminum production but suffers from high energy demands and pollution. This study investigates the aluminum chloride process as an alternative method by analyzing species behavior in AlCl<sub>3</sub>–MCl (M = Li, Na, K) molten salts at 373–473 K and 933–1033 K through quantum calculations and mathematical modeling. When initial AlCl<sub>3</sub> < 50 mol%, Cl<sup>−</sup> and AlCl<sub>4</sub><sup>−</sup> dominate at 933–1033 K, with minor temperature effects. When initial AlCl<sub>3</sub> > 50 mol%, AlCl<sub>4</sub><sup>−</sup>, Al<sub>2</sub>Cl<sub>7</sub><sup>−</sup> and Al<sub>2</sub>Cl<sub>6</sub> dominate at 373–473 K. Increasing AlCl<sub>3</sub> concentration decreases AlCl<sub>4</sub><sup>−</sup> fraction; Al<sub>2</sub>Cl<sub>7</sub><sup>−</sup> fraction peaks at 66.7 mol% AlCl<sub>3</sub> then declines; Al<sub>2</sub>Cl<sub>6</sub> fraction steadily increases. Higher temperatures promote Al<sub>2</sub>Cl<sub>7</sub><sup>−</sup> conversion to AlCl<sub>4</sub><sup>−</sup> and Al<sub>2</sub>Cl<sub>6</sub>. Redox calculations show preferential Cl<sup>−</sup> discharge at the anode when AlCl<sub>3</sub> < 50 mol%. At AlCl<sub>3</sub> > 50 mol%, Al<sup>3+</sup> in Al<sub>2</sub>Cl<sub>6</sub> discharges at the cathode and Cl<sup>−</sup> in Al<sub>2</sub>Cl<sub>7</sub><sup>−</sup> discharges at the anode.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115368"},"PeriodicalIF":3.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144623264","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Exploring the nitrogen migration mechanism during the pyrolysis of tyrosine and histidine based on density functional theory 基于密度泛函理论探讨酪氨酸和组氨酸热解过程中氮的迁移机制

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-07-08 DOI: 10.1016/j.comptc.2025.115371

Zhenqing Han , Jun Shen , Yun Guo , Shengxiang Deng , Sha Wang , Haiyong Peng , Chen Zhang , Hai Zhang

{"title":"Exploring the nitrogen migration mechanism during the pyrolysis of tyrosine and histidine based on density functional theory","authors":"Zhenqing Han , Jun Shen , Yun Guo , Shengxiang Deng , Sha Wang , Haiyong Peng , Chen Zhang , Hai Zhang","doi":"10.1016/j.comptc.2025.115371","DOIUrl":"10.1016/j.comptc.2025.115371","url":null,"abstract":"<div><div>Proteins/amino acids are the main forms of nitrogen in biomass, and the formation mechanism of NO<sub>x</sub> precursors in their pyrolysis needs to be further studied. This work investigates the specific pathway of N element migration to pyrolysis gas and pyrolysis oil during the pyrolysis of tyrosine and histidine using density functional theory (DFT) calculation method for the first time. The results indicate that due to the lowest energy barrier and highest reaction rate of the NH<sub>3</sub> formation pathway for direct removal of amino groups, the pyrolysis of tyrosine and histidine tends to generate NH<sub>3</sub> rather than HCN. Nitrile and imidazole heterocycles are the main components of tyrosine and histidine pyrolysis oil, respectively. The former is obtained through continuous dehydrogenation reactions, while the latter is generated by the adsorption of active sites caused by the dehydrogenation of imidazole intermediates and hydrocarbon compounds, or the hydrogenation decomposition of nitrogen heterocycles themselves.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115371"},"PeriodicalIF":3.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144581198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Reaction mechanism of palladium-catalyzed intramolecular cyclization/hydroamination of 1-(2-aminophenyl)-3-phenylprop-2yn-1-one, CN bond formation processes studied with DFT calculations 用DFT计算研究了钯催化1-（2-氨基苯基）-3-苯基丙烷-2 - n-1- 1- CN键形成过程的分子内环化/氢胺化反应机理

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-07-08 DOI: 10.1016/j.comptc.2025.115358

Soumia Bouchentouf , Meijuan Zhou , Majda Sekkal-Rahal , Michael Springborg

{"title":"Reaction mechanism of palladium-catalyzed intramolecular cyclization/hydroamination of 1-(2-aminophenyl)-3-phenylprop-2yn-1-one, CN bond formation processes studied with DFT calculations","authors":"Soumia Bouchentouf , Meijuan Zhou , Majda Sekkal-Rahal , Michael Springborg","doi":"10.1016/j.comptc.2025.115358","DOIUrl":"10.1016/j.comptc.2025.115358","url":null,"abstract":"<div><div>DFT calculations using the B3LYP level of theory were carried out in order to determine the mechanisms of the hydromination reaction and of the cyclization reaction of 1-(2-aminophenyl)-3-phenylprop-2yn-1-one R1. Hydromination of R1 by diethylamine leads to 2-phenylquinolin-4 (1H)-one P1, while the catalytic cyclization using different palladium complexes as catalysts leads to the production of (2Z)-2-benzylidene-1,2-dihydro-3H-indol-3-one P2. Analyzing the potential energy surface indicates that the formation of the C<img>N bond in the presence of diethylamine is related to high activation energies. In addition, the calculations show that there are two reaction paths for the palladium-catalyzed cyclization reaction of R1; the first one is of [1,6]-H shift type while the second is of [1,5]-H shift type, followed by the formation of a C<img>N bond. In each case, this is the rate-determining step. We compare the Pd complexes and determine the one with the best catalytic performance in the production of P2.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115358"},"PeriodicalIF":3.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0