{"title":"Mechanism of Formation and Decomposition of C6H5(O2•)C(OH)C6H4OH","authors":"Gregory A. Poskrebyshev","doi":"10.1002/slct.202400553","DOIUrl":null,"url":null,"abstract":"<p>In the present theoretical study, the thermochemical properties of Ph(O<sub>2</sub><sup>•</sup>)C(OH)PhOH and considered products of its oxidation are calculated using the DFT approaches (M062X, B3LYP, wB97XD, M08HX, MN15) at the 6−311++G(d, p) level of theory. The DFT values of Δ<sub>ra</sub><i>H</i><sup>o</sup>(Y<sub>i</sub>) of the atomization of considered structures are corrected using the linear calibration dependencies reported for the peroxides as well as for the hydrocarbons (including aromatic and simple oxygenated compounds). The values of Δ<sub>f</sub><i>H</i><sup>o</sup>(Y<sub>i</sub>, CORR) ± 3SD<sub>i</sub>, derived from the corrected values of Δ<sub>ra</sub><i>H</i><sup>o</sup>(Y<sub>i</sub>, CORR), are coordinated by the intersection of their 3SD<sub>i</sub> intervals, determined previously. The values of Δ<sub>f</sub><i>H</i><sup>o</sup>(Y, MEAN) ± 2SD<sub>Y</sub> of the Ph(O<sub>2</sub><sup>•</sup>)C(OH)PhOH (2F), Ph<sup>•</sup>─OO─C(OH)PhOH (3G), HOPh<sup>•</sup>─OO─C(OH)Ph (2G), PhC(OH)<sub>2</sub>PhOH (1H), Ph(O<sub>2</sub>H)C(OH)PhOH (4G) and Ph(O<sup>•</sup>)C(OH)PhOH (1G) (corresponded, respectively, to −159.4 ± 6,−55.2 ± 6,−61.5 ± 3.7,−385.8 ± 6,−293.4 ± 1.4,−148.9 ± 6 kJ/mol), as well as the values of <i>E</i><sub>a</sub><sup>‡</sup> = 127.8 ± 7, 121.2 ± 8, 17.2 ± 5, 19.4 ± 3 kJ/mol, determined, respectively, for the reactions (R21a), (R21b), (R22a), (R22b) and the values of the rate constants of associated reactions, are reported for the first time. According to calculations, the replacement of >C<sup>•</sup><b>H</b> by <b>OH</b> group increases the values of dissociation energy (DE) of >C(X)─O<sub>2</sub><b><sup>•</sup></b>, >C(X)O─O<b><sup>•</sup></b>, >C(X)O─H, PhC(X)OO─<sup>•</sup>PhOH, and HOPhC(X)OO─<sup>•</sup>Ph bonds, but decreases those values of >C(X)O<sub>2</sub><b>–</b>H, HOPhC(X)<sup>OO•</sup>Ph, and PhC(X)<sup>OO•</sup>PhOH bonds. As a result of increased stability of the >C(X)─O<sub>2</sub><b><sup>•</sup></b> bond (<i>X</i> = OH), the higher temperatures can be used for the chain production of <i>p</i>-PhC(O<sub>2</sub>H)HPhOH and <i>p</i>-PhC(O<sub>2</sub>H)(OH)PhOH at high concentrations of <i>p</i>-PhCH<sub>2</sub>PhOH. On the contrary, the contribution of reactions (R21a) and (R21b) to the oxidation is significant under low concentrations of <i>p</i>-PhCH<sub>2</sub>PhOH. Its also found that the stable intermediate O<sub>2</sub> π–π cluster, predicted for the >C<b><sup>•</sup></b>(H) radical, is not observed for the reaction of >C<b><sup>•</sup></b>(OH) with O<sub>2</sub>, due to the formation of a hydrogen bond between the OH group and partially charged O<sub>2</sub><sup>δ−</sup>.</p>","PeriodicalId":146,"journal":{"name":"ChemistrySelect","volume":"10 5","pages":""},"PeriodicalIF":1.9000,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemistrySelect","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/slct.202400553","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
In the present theoretical study, the thermochemical properties of Ph(O2•)C(OH)PhOH and considered products of its oxidation are calculated using the DFT approaches (M062X, B3LYP, wB97XD, M08HX, MN15) at the 6−311++G(d, p) level of theory. The DFT values of ΔraHo(Yi) of the atomization of considered structures are corrected using the linear calibration dependencies reported for the peroxides as well as for the hydrocarbons (including aromatic and simple oxygenated compounds). The values of ΔfHo(Yi, CORR) ± 3SDi, derived from the corrected values of ΔraHo(Yi, CORR), are coordinated by the intersection of their 3SDi intervals, determined previously. The values of ΔfHo(Y, MEAN) ± 2SDY of the Ph(O2•)C(OH)PhOH (2F), Ph•─OO─C(OH)PhOH (3G), HOPh•─OO─C(OH)Ph (2G), PhC(OH)2PhOH (1H), Ph(O2H)C(OH)PhOH (4G) and Ph(O•)C(OH)PhOH (1G) (corresponded, respectively, to −159.4 ± 6,−55.2 ± 6,−61.5 ± 3.7,−385.8 ± 6,−293.4 ± 1.4,−148.9 ± 6 kJ/mol), as well as the values of Ea‡ = 127.8 ± 7, 121.2 ± 8, 17.2 ± 5, 19.4 ± 3 kJ/mol, determined, respectively, for the reactions (R21a), (R21b), (R22a), (R22b) and the values of the rate constants of associated reactions, are reported for the first time. According to calculations, the replacement of >C•H by OH group increases the values of dissociation energy (DE) of >C(X)─O2•, >C(X)O─O•, >C(X)O─H, PhC(X)OO─•PhOH, and HOPhC(X)OO─•Ph bonds, but decreases those values of >C(X)O2–H, HOPhC(X)OO•Ph, and PhC(X)OO•PhOH bonds. As a result of increased stability of the >C(X)─O2• bond (X = OH), the higher temperatures can be used for the chain production of p-PhC(O2H)HPhOH and p-PhC(O2H)(OH)PhOH at high concentrations of p-PhCH2PhOH. On the contrary, the contribution of reactions (R21a) and (R21b) to the oxidation is significant under low concentrations of p-PhCH2PhOH. Its also found that the stable intermediate O2 π–π cluster, predicted for the >C•(H) radical, is not observed for the reaction of >C•(OH) with O2, due to the formation of a hydrogen bond between the OH group and partially charged O2δ−.
期刊介绍:
ChemistrySelect is the latest journal from ChemPubSoc Europe and Wiley-VCH. It offers researchers a quality society-owned journal in which to publish their work in all areas of chemistry. Manuscripts are evaluated by active researchers to ensure they add meaningfully to the scientific literature, and those accepted are processed quickly to ensure rapid online publication.