Journal of Physical Organic Chemistry最新文献

{"title":"Addition reaction of azoles to acetone-d6: NMR and computational studies","authors":"Rosa M. Claramunt,&nbsp;Dionisia Sanz,&nbsp;Ibon Alkorta,&nbsp;José Elguero","doi":"10.1002/poc.4612","DOIUrl":"10.1002/poc.4612","url":null,"abstract":"<p>The reactivity of imidazole, pyrazole, 1,2,4-triazole, 1,2,3-triazole, and tetrazole with acetone (propan-2-one) has been studied by ¹H and ¹³C NMR using acetone-<i>d</i>_<i>6</i> as solvent at temperatures ranging from 173 to 300 K at 10 K intervals. Simultaneously, the reaction has been theoretically calculated at the B3LYP/6-311++G(d,p) level, and experimental and theoretical results have been compared. The equilibrium constants between azoles and adducts α,α-dimethyl-azole-methanol were analyzed, assuming that the straight part of the plots –R ln <i>K</i>_e vs. 1/T can be used to determine Δ<i>H</i> and Δ<i>S</i>. Calculated and experimental data are related, but the theoretical values are proportionally higher. The tautomerism of triazoles and tetrazole has been considered in order to discuss the reactions.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.9,"publicationDate":"2024-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.4612","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141110710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular structure and conformational properties of triflamide derivatives in the gas phase—Part II: 6-Iodo-3-(triflamidomethyl)-4-triflyl-1,4,2,7-oxaazadisilepane and 2,2,4,4-tetramethyl-6,8-bis (triflyl)-3-oxa-6,8-diaza-2,4-disilabicyclo[3.2.2]nonane by gas-phase electron diffraction and theoretical calculations","authors":"Bagrat A. Shainyan,&nbsp;Alexey V. Eroshin,&nbsp;Sergey A. Shlykov","doi":"10.1002/poc.4613","DOIUrl":"10.1002/poc.4613","url":null,"abstract":"<p>6-Iodo-3-(triflamidomethyl)-4-triflyl-1,4,2,7-oxazadisilepane <b>1</b> and the product of its cyclization, 2,2,4,4-tetramethyl-6,8-bis (triflyl)-3-oxa-6,8-diaza-2,4-disilabicyclo[3.2.2]nonane <b>2</b>, have been studied by gas-phase electron diffraction and DFT calculations. The conformational equilibrium in the gas phase was shown to include three and two conformers for <b>1</b> and <b>2</b>, respectively, in contrast to only one conformer determined by single crystal X-ray diffraction. The structural analysis of the conformers was performed and the pathways of the conformational transitions were analyzed.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.9,"publicationDate":"2024-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141124574","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}

{"title":"Molecular dynamics simulation study of post-transition state bifurcation: A case study on the ambimodal transition state of dipolar/Diels–Alder cycloaddition","authors":"Tatsuhiro Murakami,&nbsp;Yuya Kikuma,&nbsp;Daiki Hayashi,&nbsp;Shunichi Ibuki,&nbsp;Shoto Nakagawa,&nbsp;Hinami Ueno,&nbsp;Toshiyuki Takayanagi","doi":"10.1002/poc.4611","DOIUrl":"10.1002/poc.4611","url":null,"abstract":"<p>The potential energy surfaces for the reactions of 1,3-butadiene with 2-hydroxythioacrolein and 2-aminoacrolein exhibit ambimodal transition states leading to both dipolar (4 + 3) and Diels–Alder (4 + 2) cycloaddition products, thereby demonstrating a post transition state bifurcation feature. We have investigated the bifurcation dynamics of these reactions using three molecular dynamics (MD) methods: quasi-classical trajectory, classical MD, and ring-polymer MD simulations. The trajectory calculations were performed with the semiempirical GFN2-xTB method with the element-specific parameters optimized to reproduce the density-functional theory calculations. The effect of water solvation was examined using an implicit solvation model, revealing significant differences in bifurcation dynamic between gas-phase and solution-phase reactions. Nuclear quantum effects were found to play a crucial role in the proton-transfer process from the (4 + 3) intermediate to the (4 + 3) product in the case of the 2-aminoacrolein reaction.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.9,"publicationDate":"2024-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.4611","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140830524","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanism of the desulfurization route of the reduction of SO2 on carbons. Dimerization of Disulfur and Tetrasulfur","authors":"Eduardo Humeres,&nbsp;Marília Isabel Tarnowski Correia,&nbsp;Nito Angelo Debacher,&nbsp;Regina de F. P. M. Moreira","doi":"10.1002/poc.4610","DOIUrl":"10.1002/poc.4610","url":null,"abstract":"<p>The desulfurization of carbons modified with SO₂ was studied as a dispersion in boiling cyclohexane (81°C) using activated carbon (mAC) and graphene oxide (mGO), modified by SO₂. The steady-state species in the carbon matrix after the catalytic reduction of SO₂ was considered a trisulfane. For mAC, there was a burst of a sulfur species identified as S₂ by UV spectrum with a maximum at 217 nm (ε_M at 217 nm = 2.56 × 10³) that showed a second-order decay of absorbance with \u0000<span></span><math>\u0000 <msub>\u0000 <mi>k</mi>\u0000 <msub>\u0000 <mi>S</mi>\u0000 <mn>2</mn>\u0000 </msub>\u0000 </msub></math> = 47.29 M^-1·sec^-1 (\u0000<span></span><math>\u0000 <msubsup>\u0000 <mi>ΔG</mi>\u0000 <mn>354</mn>\u0000 <mo>‡</mo>\u0000 </msubsup></math>= 18.1 kcal·mol^-1). The product was postulated to be S₄. No other consecutive reaction was observed because of the possible adsorption of S₄ in the carbon matrix. The desulfurization of mGO was shown by XPS and the kinetics were a second-order decay up to 16 min (\u0000<span></span><math>\u0000 <msub>\u0000 <mi>k</mi>\u0000 <msub>\u0000 <mi>S</mi>\u0000 <mn>2</mn>\u0000 </msub>\u0000 </msub>\u0000 <mo>=</mo></math> 18.41 M^-1·sec^-1;\u0000<span></span><math>\u0000 <mspace></mspace>\u0000 <msubsup>\u0000 <mi>ΔG</mi>\u0000 <mn>354</mn>\u0000 <mo>‡</mo>\u0000 </msubsup></math>= 18.8 kcal·mol^-1) followed by a second-order increase of absorbance with \u0000<span></span><math>\u0000 <msub>\u0000 <mi>k</mi>\u0000 <msub>\u0000 <mi>S</mi>\u0000 <mn>4</mn>\u0000 </msub>\u0000 </msub></math> = 3.84 M^-1·sec^-1 (\u0000<span></span><math>\u0000 <msubsup>\u0000 <mi>ΔG</mi>\u0000 <mn>354</mn>\u0000 <mo>‡</mo>\u0000 </msubsup></math>= 19.9), where the product showed a double maximum at 260-285 nm typical of S₈. These results are consistent with a mechanism of consecutive thermodynamically favorable dimerizations of S₂ and S₄ and with the desulfurization mechanism that has been previously postulated.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.9,"publicationDate":"2024-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140670345","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}

{"title":"A study of the global and local aromaticity of hetero[8]circulenes","authors":"Satewaerdi Helili,&nbsp;Ablikim Kerim","doi":"10.1002/poc.4609","DOIUrl":"10.1002/poc.4609","url":null,"abstract":"<p>The topological resonance energy (TRE) method was used to investigate the aromaticity of hetero[8]circulenes in both their neutral and doubly charged ion states. The compounds varying stabilities in different charged states were explained in terms of the topological charge stabilization rule. The TRE-based aromaticity indices were compared with those obtained by the gauge-including magnetically induced currents (GIMIC) method. However, the lack of correlation between the TRE and GIMIC aromaticity indices, as well as the contradictory trends observed, suggest that further investigation is necessary to fully understand the aromaticity of hetero[8]circulenes. We employed the circuit resonance energy (CRE) method to assess local aromaticity. Our CRE results indicate that individual benzene or heterocyclic five-membered units within the molecule maintain their strong aromatic character and serve as the primary source of global aromaticity, both in their neutral and doubly charged ion states. Although our CRE results provide valuable insights, it is important to note that there are cases where the magnitude of local aromaticity predicted by the nucleus-independent chemical shift (NICS[0] and NICS[1]) indices does not align with our CRE results.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140571180","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}

{"title":"The measurement of one-electron redox potentials of free radicals","authors":"Igor V. Khudyakov","doi":"10.1002/poc.4608","DOIUrl":"10.1002/poc.4608","url":null,"abstract":"<p>The paper is devoted to the measurements of one-electron redox potentials of transient free radicals E^o. These values can be measured in the reversible redox reactions of radicals under investigation with a reference pair, which E^o is known. Several E^o of transient radicals are presented. The convenient and important objects for E^o measurement are quinone/semiquinone radical-anions. A general problem of measurement of thermodynamic properties of short-lived transients is discussed.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140571181","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}

{"title":"Computational studies on exothermic carbon–carbon bond cleavages","authors":"Athanassios Nicolaides,&nbsp;Hideo Tomioka","doi":"10.1002/poc.4606","DOIUrl":"10.1002/poc.4606","url":null,"abstract":"<p>Structural aspects of single C<span></span>C bond dissociation energies are examined and it is shown that in certain cases a negative bond dissociation energy (BDE) implies a very weak bond and an unstable species prone to bond breaking resulting in dissociation or structural rearrangement. It is proposed that, in such cases, a better quantitative indicator for the strength of the bond is the activation energy required for its fission. <i>o</i>-Phenelylene bis(nitrene) <b>1</b> is computed to have the most negative C<span></span>C BDE for an observable species. Under cryogenic conditions, activation energy for the dissociation of this bond has been measured as only 2.8 kcal/mol, making it the weakest that we know of. An explanation based on the formation of two new bonds as responsible for this extremely weak bond is given.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140317029","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}

{"title":"Theoretical investigation of substituted end groups in thiophene-phenyl-thiophene (TPT) derivatives for high efficiency organic solar cells","authors":"Sonia Sadiq,&nbsp;Rasheed Ahmad Khera,&nbsp;Ahmed M. Tawfeek,&nbsp;Mahmoud A. A. Ibrahim,&nbsp;Faheem Abbas,&nbsp;Sajjad Ali,&nbsp;Ahmed Mahal,&nbsp;Duan Meitao,&nbsp;Muhammad Waqas","doi":"10.1002/poc.4607","DOIUrl":"10.1002/poc.4607","url":null,"abstract":"<p>The field of organic solar cells has witnessed notable advancements in the past few years, mostly due to the development of novel materials for the active layer. The current investigations reveal the potential of nine previously unexplored molecules (<b>TP1–TP9</b>) designed by end group modification of TPT4F molecule. These molecules were investigated at MPW1PW91/6-31G (d, p) with DFT and TD-DFT approach to study the various photovoltaic and geometrical parameters. The results obtained through computations indicated improvement in the investigated parameters. The terminal group modification shifted the absorption maximum towards longer wavelength in the UV-visible region. Highly conjugated modified acceptors reduced the band gap. The lower excitation energies increased the rate of charge transfer. The designed molecules showed improved excited state lifetime in comparison to the reference. The open circuit voltage was determined using the PTB7 polymer, which exhibited a noticeable improvement, especially in TP1 (1.70 eV), TP3 (1.75 eV), TP4 (1.68 eV), TP6 (1.85 eV), and TP7 (1.75 eV) when compared with reference (1.59 eV). Moreover, charge transfer investigations of designed molecules with PTB7 complex were performed by analyzing the concentration of charge transfer over molecular orbitals, that is, HOMO to LUMO. All of the preceding investigations targeted to achieve high-efficiency organic cells reveal that the altered molecules can be considered effective candidates to tackle future energy problems.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140154147","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}

{"title":"The curious case of the colored crystals of N-substituted 2-oxo-1,2-dihydropyridinyl-3-yl amines and amides: Self-association in the solid state","authors":"Wendy A. Loughlin,&nbsp;Ian D. Jenkins,&nbsp;Peter C. Healy,&nbsp;N. David Karis,&nbsp;Gregory K. Pierens","doi":"10.1002/poc.4603","DOIUrl":"10.1002/poc.4603","url":null,"abstract":"<p>During a previous investigation of pyridone derivatives as inhibitors of glycogen phosphorylase, we observed that some <i>N-</i>substituted 2-oxo-1,2-dihydropyridinyl-3-yl amines and amides exhibited different colors, ranging from red to green to blue to teal. Remarkably, one compound (compound <b>8</b>) could be crystallized in both a red form and a green form. To try to understand these observations, we have carried out further spectroscopic studies in the solid state and in solution employing UV-visible spectroscopy, NMR spectroscopy, and X-ray crystallography, along with molecular mechanics and DFT calculations on selected compounds. Evidence was obtained in the solid state for the self-association of pyridones into dimeric complexes or near-planar dimers induced by intermolecular hydrogen bonding and possible π-stacking, whereas monomeric structures for two compounds were proposed in chloroform, in agreement with the DFT calculated chemical shifts. In this study, it was determined that the colors observed could not be attributed to hydrogen bonding or possible π-bond stacking in the novel relatively unconjugated pyridone derivatives. A possible explanation for the colors is suggested: a contaminant formed by aerial oxidation of trace amounts of the 3-aminopyridone starting material. This result contrasts with existing literature reports of UV and fluorescence spectra, which indicated distinct coloration for conjugated 2-pyridone compounds. The spectroscopic results, including X-ray structural data for five pyridones, contribute to a deeper understanding of structural interactions in pyridone derivatives.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.4603","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140007482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical study on the kinetics and reaction mechanism involved in the reduction of quinone by 1-benzyl-1,4-dihydronicotinamide","authors":"Manuel E. Medina,&nbsp;Hugo A. Jiménez-Vazquez,&nbsp;Luis G. Zepeda-Vallejo,&nbsp;Ángel Trigos","doi":"10.1002/poc.4605","DOIUrl":"10.1002/poc.4605","url":null,"abstract":"<p>Although it is well known that coenzyme NAD(P)H is involved in anabolic and catabolic reactions in the living organism, there is still significant controversy over the reaction mechanism involved in this biochemical transformation. Thus, 1-benzyl-1,4-dihydronicotinamide was used as a NAD(P)H model in the reduction reaction of 1,4-benzoquinone (Q), 2,3,5,6-tetrachloro-1,4-benzoquinone, and 2,3-dicyano-1,4-benzoquinone in acetonitrile medium. The kinetic calculations support that formal hydride transfer is the main mechanism promoting Q reduction, while the two-step process dominates 2,3-dicyano-1,4-benzoquinone reduction. Interestingly, only the single-electron transfer mechanism takes place when 2,3,5,6-tetrachloro-1,4-benzoquinone is used, affording the corresponding semiquinone derivative as the main product. This mechanistic behavior is related to the presence or absence of electron-withdrawing groups in the quinones used. Furthermore, the kinetic study results showed that calculated reaction rate constants are in close agreement with experimental results. The results support that formal hydride transfer on the reduction reaction of Q by 1-benzyl-1,4-dihydronicotinamide in acetonitrile proceeds through a hydrogen coupled electron transfer mechanism. This theoretical analysis provides valuable knowledge that can be extrapolated to study the reduction of quinones performed by NADH and NADPH in physiological media.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139946536","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}