Journal of Physical Organic Chemistry最新文献_第5页

Exploring Conformational Preferences in XC(W)ZY Molecules With X, Y = F, Cl, Br and W, Z = O, S, Se: Unraveling the Influence of Conjugative and Anomeric Interactions 探索 XC(W)ZY 分子中的构象偏好，其中 X、Y = F、Cl、Br 和 W、Z = O、S、Se：揭示共轭和同分异构相互作用的影响

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-08-12 DOI: 10.1002/poc.4654

Michelle T. Custodio Castro, Carlos O. Della Védova, Rosana M. Romano

{"title":"Exploring Conformational Preferences in XC(W)ZY Molecules With X, Y = F, Cl, Br and W, Z = O, S, Se: Unraveling the Influence of Conjugative and Anomeric Interactions","authors":"Michelle T. Custodio Castro, Carlos O. Della Védova, Rosana M. Romano","doi":"10.1002/poc.4654","DOIUrl":"10.1002/poc.4654","url":null,"abstract":"<div>\u0000 \u0000 The relative stabilities of the syn- and anti-conformers of 72 molecules belonging to the XC(W)ZY type, with X, Y = F, Cl, Br and W, Z = O, S, Se, have been computed using the B3LYP/aug-cc-pVDZ approximation. The conformational preferences, represented by the energy differences between the two rotamers, exhibit a systematic trend in relation to both the halogen atoms and the chalcogen atoms. These computational predictions are in agreement with available experimental results. The NBO formalism was employed to assess the influence of both the conjugative and anomeric interactions on the relative energy of the conformers. It has been determined that the conjugative interaction provides a satisfactory explanation for the energy differences between rotamers. In contrast, the anomeric interactions favors the syn-conformation in all cases. The relative stabilities between XC(W)ZY/YC(W)ZX and XC(W)ZY/XC(Z)WY constitutional isomers have also been computed and correlated with the experimental data.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142191280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Novel Trifunctional Intramolecular Frustrated Lewis Pair Derived From Aminoboronic Acid for Converting CO2 Into Valuable Chemicals 由氨基硼酸衍生的新型三官能团分子内受托路易斯对，可将二氧化碳转化为有价值的化学品

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-08-12 DOI: 10.1002/poc.4655

Mohmmad Faizan, Guntupalli Santhosh, Madhumita Chakraborty, Ravinder Pawar

{"title":"Novel Trifunctional Intramolecular Frustrated Lewis Pair Derived From Aminoboronic Acid for Converting CO2 Into Valuable Chemicals","authors":"Mohmmad Faizan, Guntupalli Santhosh, Madhumita Chakraborty, Ravinder Pawar","doi":"10.1002/poc.4655","DOIUrl":"10.1002/poc.4655","url":null,"abstract":"<div>\u0000 \u0000 The conversion of CO2 into valuable chemicals remains a significant challenge for achieving environmental sustainability, primarily due to the stability of the CO2 molecule. This necessitates the development of efficient and ecofriendly catalysts. In recent years, frustrated Lewis pairs (FLPs) have shown promise for CO2 utilization. In this study, we introduce α-aminodiboronic acid (DBA), a novel trifunctional aminoboronic acid, as an intramolecular FLP for converting CO2 into cyclic carbonate and formic acid. Using density functional theory (DFT) calculations, we explored the reaction mechanism and investigated DBA's electronic structure through molecular electrostatic potential surface (MESP) and natural bond orbital (NBO) analyses. Our results reveal that one −B (OH)2 group induces an unusual state of frustration in the molecule due to charge transfer from the nitrogen atom's lone pair to the π* orbitals, enhancing catalytic performance. The additional −B (OH)2 group serves as an anchoring site for reactive species. The epoxide activation energy is reduced by approximately 27 kcal/mol compared to the uncatalyzed reaction, and the reduction of CO2 occurs with a requirement of 26 kcal/mol. The additional −B (OH)2 plays a crucial role in the catalytic mechanism and minimizes the energies of various structures observed in the reaction path. The reaction energetics align with structural analysis observations, marking this study as the first report on single-molecule trifunctional FLPs for transforming CO2 into valuable chemicals.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142191319","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Theoretical investigations on N2H5N5/PDO cocrystal via a first-principles study 通过第一原理研究对 N2H5N5/PDO 共晶体进行理论探索

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-08-11 DOI: 10.1002/poc.4653

Zhipeng Chen, Junqi Wang, Qingshan Xie, Chen Yang, Changlin Zhou

{"title":"Theoretical investigations on N2H5N5/PDO cocrystal via a first-principles study","authors":"Zhipeng Chen, Junqi Wang, Qingshan Xie, Chen Yang, Changlin Zhou","doi":"10.1002/poc.4653","DOIUrl":"10.1002/poc.4653","url":null,"abstract":"The exploration of cyclo-N5ˉ-based energetic cocrystals represents a noteworthy avenue within pentazolate chemistry, focusing on leveraging cocrystallization to enhance stability. Recently, a novel cocrystal explosive, N2H5N5/PDO, was developed by combining N2H5N5 with pyrazine 1,4-dioxide (PDO), exhibiting promising detonation characteristics and reduced sensitivity. This study endeavors to elucidate how the structure and noncovalent interactions impact the performance of N2H5N5/PDO through a first-principles investigation. The results indicate that the enhanced hydrogen bonding and wave-like crystal packing structure within the cocrystal effectively bolster its stability compared to N2H5N5. The N···H and O···H interactions, in conjunction with π–π interactions, emerge as critical elements driving cocrystal formation. Compared to the pure N2H5N5, the detonation performance of the cocrystal exhibits a slight decline, albeit with a noticeable reduction in sensitivity.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142191320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Torsional influences on cross-conjugated thieno[3,4-b]thiophene photochromes 扭转对交叉共轭噻吩并[3,4-b]噻吩光色团的影响

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-08-01 DOI: 10.1002/poc.4650

Nicholas P. Adams, John D. Tovar

引用次数: 0

Theoretical study of atomic electronegativity effects on the excited-state behavior of fluorescent compounds of citrinin 原子电负性对柠檬素荧光化合物激发态行为影响的理论研究

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-07-23 DOI: 10.1002/poc.4651

Yue Gao, Meiheng Lv, Zexu Cai, Yuhang Zhang, Tingting Wang, Jianyong Liu, Fangjian Shang, Wenze Li

{"title":"Theoretical study of atomic electronegativity effects on the excited-state behavior of fluorescent compounds of citrinin","authors":"Yue Gao, Meiheng Lv, Zexu Cai, Yuhang Zhang, Tingting Wang, Jianyong Liu, Fangjian Shang, Wenze Li","doi":"10.1002/poc.4651","DOIUrl":"10.1002/poc.4651","url":null,"abstract":"The present work focuses on the light-induced behavior of citrinin derivatives in relation to atomic electronegativity. A detailed theoretical study on the photophysical properties and excited-state behavior of fluorescent compounds of citrinin (Cit-O, Cit-S, and Cit-Se, with different atomic electronegativity) has been conducted, and the effect of electronegativity on the proton transfer in this system has been explained. First, the relevant hydrogen bond parameters and infrared vibrational spectra of the optimized geometrical configurations have been insightfully investigated. It is elucidated that the hydrogen bond is strengthened after photoexcitation, and it provides a driving force for excited-state intramolecular proton transfer (ESIPT). In addition, the frontier molecular orbitals were analyzed, and the intramolecular charge transfer process in all Cit systems, the phenomenon of charge redistribution, facilitates the ESIPT reaction. By constructing potential energy surfaces for different transfer paths, the atomic electronegativity impact on the ESIPT dynamical behavior of the Cit system was determined. This work clarifies the mechanism of the intramolecular proton transfer process in the excited state of citrinin molecules and complements the theoretical study of the atomic electronegativity-regulated citrinin system, which provides a corresponding theoretical basis for the design and synthesis of new luminescence-adjustable citrinin systems.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774711","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Density functional theory study on frustrated Lewis pairs catalyzed C-H activation of heteroarenes: Mechanism variation tuning by electronic effect 关于受挫路易斯对催化的杂环烯 C-H 活化的密度泛函理论研究：电子效应对机理变化的调整

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-07-22 DOI: 10.1002/poc.4652

Youxiang Shao, Kang Xiao, Huize Wang, Yalan Liu

{"title":"Density functional theory study on frustrated Lewis pairs catalyzed C-H activation of heteroarenes: Mechanism variation tuning by electronic effect","authors":"Youxiang Shao, Kang Xiao, Huize Wang, Yalan Liu","doi":"10.1002/poc.4652","DOIUrl":"10.1002/poc.4652","url":null,"abstract":"Unreactive C-H bond activation is a new horizon for frustrated Lewis pairs (FLPs) chemistry. Although concerted mechanism (Science 2015, 349, 513) and stepwise carbene mechanism (Org. Lett. 2018, 20, 1102) have been proposed for the FLPs catalyzed C-H bond activation of 1-methylpyrrole, the influence of electronic properties of FLPs on the reaction mechanism is far away from well-understood. In this study, an assortment of P-B type FLPs with different electronic characteristic was employed to study the catalyzed C-H bond activation of 1-methylpyrrole by using density functional theory calculations. Detailed calculations demonstrated that the reactivity variation and the reaction mechanism binary of FLPs catalyzed C-H activation can be varied by tuning electronic effect of Lewis base center. On the one hand, the concerted C-H activation reactivity is mainly controlled by the electron donation of the lone pair of Lewis base center; thus, the FLPs with electron-donating substituents (FLP1, FLP2, and FLP3) catalyzed the C-H bond activation through concerted mechanism. On the other hand, the reactivity of stepwise carbene mechanism is mostly attributed to the vacant orbital of Lewis acid center; as a result, the FLP5 bearing -P(C6F5)2 preferred to catalyzed the bond activation through concerted mechanism. In contrast, a metathesis mechanism through strained four-membered ring transition state is less feasible. These results should provide deeper insight and broader perspective to understand the structure and function of FLPs for rational design of FLPs catalyzed C-H bond activation.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 10","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Computational comparison of paratropicity trends in antiaromatic s-indacene derivatives: Does the functional “make all the difference”? 计算比较反芳香族 s-indacene 衍生物的同位趋势：功能是否 "决定一切"？

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-07-16 DOI: 10.1002/poc.4648

Michael P. Miller, Michael M. Haley

引用次数: 0

Positive charge delocalization and anti-aromaticity of cations generated by protonation of benzo[a]fluoranthenes in superacid 苯并[a]荧蒽在超酸中质子化产生的阳离子的正电荷分散和反芳香性

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-07-14 DOI: 10.1002/poc.4647

Takao Okazaki, Haruki Yamashita, Toshikazu Kitagawa

{"title":"Positive charge delocalization and anti-aromaticity of cations generated by protonation of benzo[a]fluoranthenes in superacid","authors":"Takao Okazaki, Haruki Yamashita, Toshikazu Kitagawa","doi":"10.1002/poc.4647","DOIUrl":"10.1002/poc.4647","url":null,"abstract":"Benzo[a]fluoranthene (4a) is one of non-alternate polycyclic aromatic hydrocarbons. A reaction of 4a in CF3SO3H yielded a dark yellow solution. Direct NMR observation indicated the exclusive formation of carbocation 4aH+ by protonation at the C(8) position. The most deshielded 1H and 13C signals were observed at 8.99 ppm for H(12) and 8.29 ppm for H(1), 182.6 ppm for C(12b), 155.6 ppm for C(8a), and 149.4 ppm for C(7a). The signals for H(4) and H(5) were significantly more shielded than those of 4a. A reaction of 3-tert-butylbenzo[a]fluoranthene (4b) in CF3SO3H afforded carbocation 4bH+ by the protonation at the C(8) position. 4bH+ was gradually converted to 4aH+. The changes in 13C NMR chemical shifts (Δδ13C) suggested that positive charge was delocalized into mainly seven carbons in 4aH+ and 4bH+. The observed cations were found to be the most stable cations among the possible protonation cations by the DFT method. The NICS(1)zz values for the five-membered rings were calculated to be 35.6 for 4aH+ and 34.4 for 4bH+ by GIAO-B3LYP/6-311+G(2d,p). The experimental NMR and the NICS(1)zz data indicated that the five-membered rings in 4aH+ and 4bH+ exhibited anti-aromaticity.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 10","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141650513","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Influence of halogen substituents on sensitivity towards detonation of polycyclic nitroaromatic high-energy molecules 卤素取代基对多环硝基芳香族高能分子引爆敏感性的影响

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-07-12 DOI: 10.1002/poc.4649

Ivana S. Veljković, Aleksandra B. Đunović, Dušan Ž. Veljković

引用次数: 0

Exploring the specific chemistries of the cycloaddition reactions of 5-benzoyl-3(2H)-isothiazolone and stable nitrile oxides: Insights from Density Functional Theory analysis 探索 5-苯甲酰基-3(2H)-异噻唑酮和稳定腈氧化物环化反应的特殊化学性质：密度泛函理论分析的启示

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2024-07-11 DOI: 10.1002/poc.4645

Muntaka Is-mail, Albert Aniagyei, Caroline R. Kwawu, Gabriel Amankwah, Elliot Menkah, Evans Adei

{"title":"Exploring the specific chemistries of the cycloaddition reactions of 5-benzoyl-3(2H)-isothiazolone and stable nitrile oxides: Insights from Density Functional Theory analysis","authors":"Muntaka Is-mail, Albert Aniagyei, Caroline R. Kwawu, Gabriel Amankwah, Elliot Menkah, Evans Adei","doi":"10.1002/poc.4645","DOIUrl":"10.1002/poc.4645","url":null,"abstract":"Isothiazolones are important heterocyclics with pharmacological potency such as anti-inflammatory, anticancer, antimicrobial, and robust biocidal (used in agrochemicals). This study seeks to provide mechanistic insight into the chemo- and regio-selectivities of the [3 + 2] cycloaddition reaction of 5-benzoyl-3(2H)-isothiazolone (A1) with two stable nitrile oxides, that is, mesitonitrile oxide (A2) and dichlorobenzonitrile oxide (A3) using M06-2X hybrid density functional calculations coupled with the 6-311G (d, p) basis sets. Mesitonitrile oxide A2 chemo-selectively adds across the carbonyl of the benzyl group of A1 while dichloro benzonitrile oxide A3 preferentially adds across the ethylene center of A1. Derivatization of A1 with electron-donating groups lowers the activation barriers by a very minute margin ranging from 0.1 to 0.5 kcal/mol whereas electron-withdrawing groups significantly decrease the energetics of the reaction by a margin of 1.1 to 2.5 kcal/mol. Solvation with chloroform does not affect the selectivity of the reaction but tends to increase both activation and reaction energies of the various routes. Analysis of the Parr function on different reactive sites of A1 shows the addition of A2 via the atomic center with the largest Mullikan atomic spin densities. Substitution of the S-heteroatom with C, O, or N does not affect the regioselectivity of the reaction but lowers the activation energies in the reaction of A1 with A3. The global electron density transfer (GEDT) values predict a polar reaction between A1 and A2 whereas the reaction of A1 and A3 is non-polar.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 10","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141614088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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