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Articles de revues sur le sujet « Homolysis »

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Auteur : Grafiati
Publié le 25 mai 2024

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1

Zhang, Chen, Junxia Pi, Shu Chen, Ping Liu et Peipei Sun. « Construction of a 4H-pyrido[4,3,2-gh]phenanthridin-5(6H)-one skeleton via a catalyst-free radical cascade addition/cyclization using azo compounds as radical sources ». Organic Chemistry Frontiers 5, no 5 (2018) : 793–96. http://dx.doi.org/10.1039/c7qo00926g.

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The new radical addition/cyano insertion/homolytic aromatic substitution cascade reaction initiated by the thermal homolysis of azo compounds under catalyst-free conditions produced polycyclic phenanthridine derivatives.
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2

Shin, Jeongcheol, Jiseon Lee, Jong-Min Suh et Kiyoung Park. « Ligand-field transition-induced C–S bond formation from nickelacycles ». Chemical Science 12, no 48 (2021) : 15908–15. http://dx.doi.org/10.1039/d1sc05113j.

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d–d excitations can accelerate C–S reductive eliminations of nickelacycles via intersystem crossing to a repulsive 3(C-to-Ni charge transfer) state inducing Ni–C bond homolysis. This homolytic photoreactivity is common for organonickel(ii) complexes.
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3

Qianzhu, Haocheng, Wenjuan Ji, Xinjian Ji, Leixia Chu, Chuchu Guo, Wei Lu, Wei Ding, Jiangtao Gao et Qi Zhang. « Reactivity of the nitrogen-centered tryptophanyl radical in the catalysis by the radical SAM enzyme NosL ». Chemical Communications 53, no 2 (2017) : 344–47. http://dx.doi.org/10.1039/c6cc08869d.

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The nitrogen-centered tryptophanyl radical produced by the radical SAM enzyme NosL can undergo both Cα–Cβ and Cα–C homolytic cleavages, and we show that the Cα–Cβ homolysis is energetically more favorable. The kinetics of NosL catalysis are also reported in this Communication.
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4

Ishihara, Koji, et Thomas Wilson Swaddle. « The pressure dependence of rates of homolytic fission of metal–ligand bonds in aqueous solution ». Canadian Journal of Chemistry 64, no 11 (1 novembre 1986) : 2168–70. http://dx.doi.org/10.1139/v86-356.

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The volume of activation for the exclusively homolytic decomposition of protonated 4-pyridylmethylchromium(III) ion in aqueous HClO4 at 63.4 °C is +19 cm3 mol−1, with negligible dependence on pressure up to 350 MPa at least. The origins of the strongly positive volumes of activation that characterize homolysis of complex cations in aqueous solution are examined.
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5

Yorimitsu, Hideki. « Homolytic substitution at phosphorus for C–P bond formation in organic synthesis ». Beilstein Journal of Organic Chemistry 9 (28 juin 2013) : 1269–77. http://dx.doi.org/10.3762/bjoc.9.143.

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Organophosphorus compounds are important in organic chemistry. This review article covers emerging, powerful synthetic approaches to organophosphorus compounds by homolytic substitution at phosphorus with a carbon-centered radical. Phosphination reagents include diphosphines, chalcogenophosphines and stannylphosphines, which bear a weak P–heteroatom bond for homolysis. This article deals with two transformations, radical phosphination by addition across unsaturated C–C bonds and substitution of organic halides.
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6

Cameron, Dale R., Alison M. P. Borrajo, Gregory R. J. Thatcher et Brian M. Bennett. « Organic nitrates, thionitrates, peroxynitrites, and nitric oxide : a molecular orbital study of the (X = O, S) rearrangement, a reaction of potential biological significance ». Canadian Journal of Chemistry 73, no 10 (1 octobre 1995) : 1627–38. http://dx.doi.org/10.1139/v95-202.

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The rearrangement of organic thionitrate to sulfenyl nitrite potentially mediates the release of nitric oxide from organic nitrates, such as nitroglycerin, in the presence of thiol. The biological activity of these nitrovasodilators is proposed to result from release of nitric oxide in vivo. The thionitrate rearrangement bears analogy to the rearrangement of peroxynitrous acid to nitric acid, which has been proposed to mediate the biological toxicity of nitric oxide and superoxide. In this paper, the two concerted rearrangement processes and competing homolytic reactions are explored using molecular orbital calculations at levels up to MP4SDQ/6-31G*//MP2/6-31G*. Examination of structure and energy for all conformers and isomers of RSONO2 (R = H, Me), models for organic thionitrates and their isomers, demonstrates that structures corresponding to thionitrates and sulfenyl nitrates are of similar energy. Free energies of reaction for homolysis of these compounds are low (ΔG0 < 19 kcal/mol), whereas the barrier for concerted rearrangement is large (ΔG≠(aq.) = 56 kcal/mol). The larger barrier for concerted rearrangement of peroxynitrous acid to nitric acid (ΔG≠(aq.) = 60 kcal/mol) again compares unfavourably with homolysis (ΔG0 < 11 kcal/mol for homolysis to NO2 or •NO). The transition state structures, confirmed by normal mode and intrinsic reaction coordinate analysis, indicate that considerable structural reorganization is required for concerted rearrangement of the ground state species. These results suggest that concerted rearrangement is not likely to be a viable step in either biological process. However, rearrangement via homolysis and radical recombination may provide an energetically accessible pathway for peroxynitrous acid rearrangement to nitric acid and rearrangement of thionitrate to sulfenyl nitrite. In this case, NO2 will be a primary product of both reactions. Keywords: thionitrate, nitric oxide, peroxynitrite, nitrovasodilator, nitrate.
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7

Edeleva, Mariya, Gerard Audran, Sylvain Marque et Elena Bagryanskaya. « Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations ». Materials 12, no 5 (26 février 2019) : 688. http://dx.doi.org/10.3390/ma12050688.

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Because alkoxyamines are employed in a number of important applications, such as nitroxide-mediated polymerization, radical chemistry, redox chemistry, and catalysis, research into their reactivity is especially important. Typically, the rate of alkoxyamine homolysis is strongly dependent on temperature. Nonetheless, thermal regulation of such reactions is not always optimal. This review describes various ways to reversibly change the rate of C–ON bond homolysis of alkoxyamines at constant temperature. The major methods influencing C–ON bond homolysis without alteration of temperature are protonation of functional groups in an alkoxyamine, formation of metal–alkoxyamine complexes, and chemical transformation of alkoxyamines. Depending on the structure of an alkoxyamine, these approaches can have a significant effect on the homolysis rate constant, by a factor of up to 30, and can shorten the half-lifetime from days to seconds. These methods open new prospects for the application of alkoxyamines in biology and increase the safety of (and control over) the nitroxide-mediated polymerization method.
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8

Shu, Xing-Zhong, et Xiaobo Pang. « Titanium : A Unique Metal for Radical Dehydroxylative Functionalization of Alcohols ». Synlett 32, no 13 (4 mars 2021) : 1269–74. http://dx.doi.org/10.1055/a-1406-0484.

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AbstractThe dehydroxylative functionalization of alcohols is synthetic appealing, but it remains a long-term challenge in the synthetic community. Low-valent titanium has shown the power to produce carbon radicals from alcohols via homolytic cleavage of the C–OH bonds and thus offers the potential to overcome this problem. In this perspective manuscript, we summarized the recent advance on radical dehydroxylative transformation of alcohols either promoted or catalyzed by titanium. The limitation and outlook of the studies in this field are also provided.1 Introduction2 Recent Developments in Dehydroxylative Functionalization of Alcohols2.1 Stoichiometric Titanium Complexes Mediated Homolysis of Alcohols2.2 Radical Dehydroxylative Functionalization of Alcohols by Ti Catalysis3 Summary and Outlook
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9

Koppenol, Willem H., et Reinhard Kissner. « Can ONOOH Undergo Homolysis ? » Chemical Research in Toxicology 11, no 2 (février 1998) : 87–90. http://dx.doi.org/10.1021/tx970200x.

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10

Turrà, Natascia, Ulrich Neuenschwander et Ive Hermans. « Molecule-Induced Peroxide Homolysis ». ChemPhysChem 14, no 8 (4 avril 2013) : 1666–69. http://dx.doi.org/10.1002/cphc.201300130.

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11

Milne, Paul H., Danial D. M. Wayner, Dayal P. DeCosta et James A. Pincock. « Substituent and charge distribution effects on the redox potentials of radicals. Thermodynamics for homolytic versus heterolytic cleavage in the 1-naphthylmethyl system ». Canadian Journal of Chemistry 70, no 1 (1 janvier 1992) : 121–27. http://dx.doi.org/10.1139/v92-021.

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The electrochemical oxidation and reduction potentials of a number of substituted 1-methylnaphthalenes (1a-l) and 1-naphthylmethyl radicals (2a-l•) as well as 2-methylnaphthalene (3) and the 2-naphthylmethyl radical (4•) have been measured by cyclic voltammetry and photomodulation voltammetry. The oxidation potentials correlate with σ+ (ρ+ = −7.1 and −8.4 for 1 and 2• respectively) while the reduction potentials correlate with σ− (ρ− = 10.1 and 13.0 for 1 and 2• respectively). The relative magnitude of the ρ values can be rationalized when the charge density distribution in these systems is considered. This leads to the interesting conclusion that even though a full charge is placed in the π-system of 1 when it is oxidized or reduced, the fraction of the charge that accumulates at C4 is actually less than in 2+ or 2− where only 50–70% of the charge is delocalized into the ring. A correlation between ρ for the redox reactions of 1, 2•, benzyl, diphenylmethyl, and cumyl and the calculated (AM1) charge density at C4 is established, implying that the sensitivity of the corresponding ions to substituent effects increases as the fraction of charge at that site increases. The redox data have been used in thermochemical cycles in order to estimate the substituent effect on the homolytic, mesolytic, and heterolytic cleavage reactions of 1 and its corresponding radical ions. The implication of these results on the C—C cleavage versus deprotonation of radical cations and on the photochemical homolysis versus heterolysis of naphthylmethyl halides and acetates is discussed. Keywords: electrochemistry, homolysis, heterolysis, naphthylmethyl, substituent effect.
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12

Guselnikova, Olga, Gérard Audran, Jean-Patrick Joly, Andrii Trelin, Evgeny V. Tretyakov, Vaclav Svorcik, Oleksiy Lyutakov, Sylvain R. A. Marque et Pavel Postnikov. « Establishing plasmon contribution to chemical reactions : alkoxyamines as a thermal probe ». Chemical Science 12, no 11 (2021) : 4154–61. http://dx.doi.org/10.1039/d0sc06470j.

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13

Steffan, Carl R., James H. Espenson et Andreja Bakac. « Oxidative homolysis of organochromium macrocycles ». Inorganic Chemistry 30, no 5 (mars 1991) : 1134–37. http://dx.doi.org/10.1021/ic00005a046.

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14

Edeleva, Mariya, Denis Morozov, Dmitriy Parkhomenko, Yulia Polienko, Anna Iurchenkova, Igor Kirilyuk et Elena Bagryanskaya. « Versatile approach to activation of alkoxyamine homolysis by 1,3-dipolar cycloaddition for efficient and safe nitroxide mediated polymerization ». Chemical Communications 55, no 2 (2019) : 190–93. http://dx.doi.org/10.1039/c8cc08541b.

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15

Chang, Mu-Chieh, Kate A. Jesse, Alexander S. Filatov et John S. Anderson. « Reversible homolytic activation of water via metal–ligand cooperativity in a T-shaped Ni(ii) complex ». Chemical Science 10, no 5 (2019) : 1360–67. http://dx.doi.org/10.1039/c8sc03719a.

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16

HUHTA, Marja S., Hao-Ping CHEN, Craig HEMANN, C. Russ HILLE et E. Neil G. MARSH. « Protein–coenzyme interactions in adenosylcobalamin-dependent glutamate mutase ». Biochemical Journal 355, no 1 (26 février 2001) : 131–37. http://dx.doi.org/10.1042/bj3550131.

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Glutamate mutase catalyses an unusual isomerization involving free-radical intermediates that are generated by homolysis of the cobalt–carbon bond of the coenzyme adenosylcobalamin (coenzyme B12). A variety of techniques have been used to examine the interaction between the protein and adenosylcobalamin, and between the protein and the products of coenzyme homolysis, cob(II)alamin and 5′-deoxyadenosine. These include equilibrium gel filtration, isothermal titration calorimetry, and resonance Raman, UV-visible and EPR spectroscopies. The thermodynamics of adenosylcobalamin binding to the protein have been examined and appear to be entirely entropy-driven, with ∆S = 109 Jċmol-1ċK-1. The cobalt–carbon bond stretching frequency is unchanged upon coenzyme binding to the protein, arguing against a ground-state destabilization of the cobalt–carbon bond of adenosylcobalamin by the protein. However, reconstitution of the enzyme with cob(II)alamin and 5′-deoxyadenosine, the two stable intermediates formed subsequent to homolysis, results in the blue-shifting of two of the bands comprising the UV-visible spectrum of the corrin ring. The most plausible interpretation of this result is that an interaction between the protein, 5′-deoxyadenosine and cob(II)alamin introduces a distortion into the ring corrin that perturbs its electronic properties.
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17

Sunada, Yusuke, Shintaro Ishida, Fumiya Hirakawa, Yoshihito Shiota, Kazunari Yoshizawa, Shinji Kanegawa, Osamu Sato, Hideo Nagashima et Takeaki Iwamoto. « Persistent four-coordinate iron-centered radical stabilized by π-donation ». Chemical Science 7, no 1 (2016) : 191–98. http://dx.doi.org/10.1039/c5sc02601f.

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18

Zhang, Sheng Jian, et Ying Xian Zhao. « Kinetics and Selectivity of Cyclohexane Pyrolysis ». Advanced Materials Research 455-456 (janvier 2012) : 540–48. http://dx.doi.org/10.4028/www.scientific.net/amr.455-456.540.

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Pyrolysis of cyclohexane was conducted with a plug-flow tube reactor at 873 K. The data of feed conversion fit first-order kinetics adequately, giving the apparent rate constant of 0.0092 s-1 . A chain mechanism of free radical reactions is proposed to interpret consumption of cyclohexane by four processes: homolysis of C-C bond (Path I) and homolysis of C-H bond (Path II ) in reaction chain initiation, H-abstraction of various radicals from feed molecule in reaction chain propagation (Path III ), and the process associated with coke formation (Path IV). The reaction path probability ratio of X I：X II：X III ：X IV was 0.5420: 0.0045 : 0.3897 : 0.0638.
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19

Cherkasov, Sergey, Dmitriy Parkhomenko, Alexander Genaev, Georgii Salnikov, Mariya Edeleva, Denis Morozov, Tatyana Rybalova, Igor Kirilyuk, Sylvain R. A. Marque et Elena Bagryanskaya. « NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines ». Molecules 25, no 21 (1 novembre 2020) : 5080. http://dx.doi.org/10.3390/molecules25215080.

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Three alkoxyamines based on imidazoline radicals with a pyridine functional group—potential initiators of nitroxide-mediated, controlled radical polymerization—were synthesized. Electron Paramagnetic Resonance (EPR) measurements reveal biexponential kinetics for the thermolysis for diastereomeric alkoxyamines and monoexponential kinetics for an achiral alkoxyamine. For comparison, the thermolysis of all three alkoxyamines was studied by NMR in the presence of three different scavengers, namely tetramethylpiperidine-N-oxyl (TEMPO), thiophenol (PhSH), and β-mercaptoethanol (BME), and detailed analysis of products was performed. NMR differentiates between N-inversion, epimerization, and homolysis reactions. The choice of scavenger is crucial for making a reliable and accurate estimate of the true homolysis rate constant.
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20

Zhang, Ze Ping, Yan Lu, Min Zhi Rong et Ming Qiu Zhang. « A thermally remendable and reprocessable crosslinked methyl methacrylate polymer based on oxygen insensitive dynamic reversible C–ON bonds ». RSC Advances 6, no 8 (2016) : 6350–57. http://dx.doi.org/10.1039/c5ra22275c.

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21

Zhao, Bo, Ju-You Lu, Yang Li, Dong-Huai Tu, Zhao-Tie Liu, Zhong-Wen Liu et Jian Lu. « Regioisomerized atom transfer radical addition (ATRA) of olefins with dichlorofluorocarbons ». RSC Advances 5, no 123 (2015) : 101412–15. http://dx.doi.org/10.1039/c5ra19244g.

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22

Audran, Gérard, Raphael Bikanga, Paul Brémond, Mariya Edeleva, Jean-Patrick Joly, Sylvain R. A. Marque, Paulin Nkolo et Valérie Roubaud. « How intramolecular hydrogen bonding (IHB) controls the C–ON bond homolysis in alkoxyamines ». Organic & ; Biomolecular Chemistry 15, no 39 (2017) : 8425–39. http://dx.doi.org/10.1039/c7ob02223a.

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23

Li, Hong Zhi, Lin Li, Zi Yan Zhong, Yi Han, LiHong Hu et Ying Hua Lu. « An Accurate and Efficient Method to Predict Y-NO Bond Homolysis Bond Dissociation Energies ». Mathematical Problems in Engineering 2013 (2013) : 1–10. http://dx.doi.org/10.1155/2013/860357.

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The paper suggests a new method that combines the Kennard and Stone algorithm (Kenstone, KS), hierarchical clustering (HC), and ant colony optimization (ACO)-based extreme learning machine (ELM) (KS-HC/ACO-ELM) with the density functional theory (DFT) B3LYP/6-31G(d) method to improve the accuracy of DFT calculations for the Y-NO homolysis bond dissociation energies (BDE). In this method, Kenstone divides the whole data set into two parts, the training set and the test set; HC and ACO are used to perform the cluster analysis on molecular descriptors; correlation analysis is applied for selecting the most correlated molecular descriptors in the classes, and ELM is the nonlinear model for establishing the relationship between DFT calculations and homolysis BDE experimental values. The results show that the standard deviation of homolysis BDE in the molecular test set is reduced from 4.03 kcal mol−1calculated by the DFT B3LYP/6-31G(d) method to 0.30, 0.28, 0.29, and 0.32 kcal mol−1by the KS-ELM, KS-HC-ELM, and KS-ACO-ELM methods and the artificial neural network (ANN) combined with KS-HC, respectively. This method predicts accurate values with much higher efficiency when compared to the larger basis set DFT calculation and may also achieve similarly accurate calculation results for larger molecules.
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24

Zheng, Yue, Qian-Xiong Zhou, Yang-Yang Zhang, Chao Li, Yuan-Jun Hou et Xue-Song Wang. « Substituent effect and wavelength dependence of the photoinduced Ru–O homolysis in the [Ru(bpy)2(py-SO3)]+-type complexes ». Dalton Transactions 45, no 7 (2016) : 2897–905. http://dx.doi.org/10.1039/c5dt03694a.

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25

Li, Jun, Yang Yang, Ping Zhang, James R. Sounik et Malcolm E. Kenney. « Synthesis, properties and drug potential of the photosensitive alkyl- and alkylsiloxy-ligated silicon phthalocyanine Pc 227 ». Photochem. Photobiol. Sci. 13, no 12 (2014) : 1690–98. http://dx.doi.org/10.1039/c4pp00321g.

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26

Gong, Xianyun, Hongjun Kang, Yuyan Liu et Songquan Wu. « Decomposition mechanisms and kinetics of amine/anhydride-cured DGEBA epoxy resin in near-critical water ». RSC Advances 5, no 50 (2015) : 40269–82. http://dx.doi.org/10.1039/c5ra03828f.

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27

Fokin, Andrey A., Boryslav A. Tkachenko, Oleg I. Korshunov, Pavel A. Gunchenko et Peter R. Schreiner. « Molecule-Induced Alkane Homolysis with Dioxiranes ». Journal of the American Chemical Society 123, no 45 (novembre 2001) : 11248–52. http://dx.doi.org/10.1021/ja0158096.

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28

Sturzbecher-Höhne, Manuel, Thomas Nauser, Reinhard Kissner et Willem H. Koppenol. « Photon-Initiated Homolysis of Peroxynitrous Acid ». Inorganic Chemistry 48, no 15 (3 août 2009) : 7307–12. http://dx.doi.org/10.1021/ic900614e.

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29

Gaudel-Siri, Anouk, Didier Siri et Paul Tordo. « Homolysis ofN-alkoxyamines : A Computational Study ». ChemPhysChem 7, no 2 (6 février 2006) : 430–38. http://dx.doi.org/10.1002/cphc.200500308.

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30

Song, Wenjing, et Andreja Bakac. « Oxidative Homolysis of a Nitrosylchromium Complex ». Chemistry - A European Journal 14, no 16 (29 mai 2008) : 4906–12. http://dx.doi.org/10.1002/chem.200701750.

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31

Audran, Gerard, Matisse Batsiandzy Ibanou, Paul Brémond, Jean-Patrick Joly et Sylvain R. A. Marque. « Part 10 : chemically triggered alkoxyamine C–ON bond homolysis in ionic liquid solvents ». RSC Advances 5, no 93 (2015) : 76660–65. http://dx.doi.org/10.1039/c5ra13899j.

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32

Koirala, Agni Raj, Son Docao et Kyung Byung Yoon. « Photocatalytic homolysis of methyl formate to dry formaldehyde on PdO/TiO2 : photocatalytic reverse Tishchenko reaction of methyl formate ». RSC Adv. 4, no 63 (2014) : 33144–48. http://dx.doi.org/10.1039/c4ra05744a.

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33

Nkolo, Paulin, Gérard Audran, Raphael Bikanga, Paul Brémond, Sylvain R. A. Marque et Valérie Roubaud. « C–ON bond homolysis of alkoxyamines : when too high polarity is detrimental ». Organic & ; Biomolecular Chemistry 15, no 29 (2017) : 6167–76. http://dx.doi.org/10.1039/c7ob01312d.

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In this article, previous multi-parameter linear relationships are amended using a parabolic model to describe the effect of EWGs in the alkyl fragment of alkoxyamines on the homolysis rate constant kd.
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34

Nesterova, Oksana V., Maxim L. Kuznetsov, Armando J. L. Pombeiro, Georgiy B. Shul'pin et Dmytro S. Nesterov. « Homogeneous oxidation of C–H bonds with m-CPBA catalysed by a Co/Fe system : mechanistic insights from the point of view of the oxidant ». Catalysis Science & ; Technology 12, no 1 (2022) : 282–99. http://dx.doi.org/10.1039/d1cy01991k.

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A Co/Fe system efficiently catalyses the oxidation of C–H bonds with m-CPBA. The nitric acid promoter hampers the m-CPBA homolysis, suppressing the free radical activity. Experimental and computational data evidence a concerted oxidation mechanism.
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35

Audran, Gérard, Lionel Bosco, Paul Brémond, Natacha Jugniot, Sylvain R. A. Marque, Philippe Massot, Philippe Mellet et al. « Enzymatic triggering of C–ON bond homolysis of alkoxyamines ». Organic Chemistry Frontiers 6, no 21 (2019) : 3663–72. http://dx.doi.org/10.1039/c9qo00899c.

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Alkoxyamine 1 is selectively hydrolyzed by chymotrypsin and substilisin A into alkoxyamine 2H+ for which C–ON bond homolysis occurred with a 4-fold increase in rate constants compared to 1 while non-specific proteases had no effect.
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36

Audran, Gérard, Elena Bagryanskaya, Irina Bagryanskaya, Mariya Edeleva, Jean-Patrick Joly, Sylvain R. A. Marque, Anna Iurchenkova et al. « How intramolecular coordination bonding (ICB) controls the homolysis of the C–ON bond in alkoxyamines ». RSC Advances 9, no 44 (2019) : 25776–89. http://dx.doi.org/10.1039/c9ra05334d.

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Because the C–ON bond homolysis rate constant kd is an essential parameter of alkoxyamine reactivity, it is especially important to tune kd without a major alteration of the structure of the molecule.
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37

Torti, Edoardo, Gioia Della Giustina, Stefano Protti, Daniele Merli, Giovanna Brusatin et Maurizio Fagnoni. « Aryl tosylates as non-ionic photoacid generators (PAGs) : photochemistry and applications in cationic photopolymerizations ». RSC Advances 5, no 42 (2015) : 33239–48. http://dx.doi.org/10.1039/c5ra03522h.

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Irradiation of aryl tosylates leads to homolysis of the ArO–S bond and PTSA or p-toluenesulfinic acid was released. The aryl sulfonates tested were then used as non-ionic photoacid generators (PAGs) in hybrid organic/inorganic sol–gel photoresists.
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38

Audran, Gérard, Elena Bagryanskaya, Irina Bagryanskaya, Paul Brémond, Mariya Edeleva, Sylvain R. A. Marque, Dmitriy Parkhomenko, Evgeny Tretyakov et Svetlana Zhivetyeva. « C–ON bond homolysis of alkoxyamines triggered by paramagnetic copper(ii) salts ». Inorganic Chemistry Frontiers 3, no 11 (2016) : 1464–72. http://dx.doi.org/10.1039/c6qi00277c.

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Pyridine-based alkoxyamines were used as ligands for Cu(hfac)2 to prepare the first metallic complexes of alkoxyamines. Structures of complexes were determined by X-ray analysis and a 21-fold increase in the C–ON bond homolysis was observed.
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Williams, G. K., et T. B. Brill. « Thermal Decomposition of Energetic Materials 70 : Kinetics of Organic Peroxide Decomposition Derived from the Filament Control Voltage of T-Jump/FT-IR Spectroscopy ». Applied Spectroscopy 51, no 3 (mars 1997) : 423–27. http://dx.doi.org/10.1366/0003702971940314.

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An evaluation is made about whether T-jump/FT-IR spectroscopy can be used to determine the decomposition kinetics (Arrhenius Ea and ln A parameters) of energetic organic peroxides at high temperature following very rapid heating. Polystyrene peroxide (PSP) and benzoyl peroxide were investigated, but PSP was chosen for detailed study because of its known, simple, decomposition process. The shape of the control voltage trace of the Pt filament yields kinetic constants which are reasonable for O–O bond homolysis as the rate-determining step: Ea = 39 kcal/mol, ln ( A, s−1) = 45.9. These Arrhenius parameters differ from values measured by other methods, but it is found that an isokinetic temperature of 400 ± 20 K exists for all measurements. Thus, all the kinetic measurements appear to reflect the same dominant process (O–O homolysis), but their differences make extrapolation of the rates from the temperature range of measurement to another range inaccurate.
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Poli, Rinaldo. « A journey into metal–carbon bond homolysis ». Comptes Rendus. Chimie 24, no 1 (26 avril 2021) : 147–75. http://dx.doi.org/10.5802/crchim.73.

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Venneri, Paul C., et John Warkentin. « Homolysis of Carbenes. Free Radicals from Dialkoxycarbenes ». Journal of the American Chemical Society 120, no 43 (novembre 1998) : 11182–83. http://dx.doi.org/10.1021/ja982566h.

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Blau, Reed J., et James H. Espenson. « Homolysis and electron-transfer reactions of benzylcobalamin ». Journal of the American Chemical Society 107, no 12 (juin 1985) : 3530–33. http://dx.doi.org/10.1021/ja00298a021.

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Kelley, Douglas G., Adam Marchaj, Andreja Bakac et James H. Espenson. « Formation and homolysis of organonickel(III) complexes ». Journal of the American Chemical Society 113, no 20 (septembre 1991) : 7583–87. http://dx.doi.org/10.1021/ja00020a020.

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Zhulin, V. M., T. V. Lipovich et V. L. Antonovskii. « Homolysis of dicyclohexyl peroxydicarbonate at various pressures ». Bulletin of the Academy of Sciences of the USSR Division of Chemical Science 37, no 7 (juillet 1988) : 1338–42. http://dx.doi.org/10.1007/bf00962735.

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Bakac, Andreja, James H. Espenson et James A. Janni. « Oxidative homolysis of the superoxopentaaquachromium(III)ion ». Journal of the Chemical Society, Chemical Communications, no 3 (1994) : 315. http://dx.doi.org/10.1039/c39940000315.

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Beaudoin, Emmanuel, Denis Bertin, Didier Gigmes, Sylvain R. A. Marque, Didier Siri et Paul Tordo. « Alkoxyamine C–ON Bond Homolysis : Stereoelectronic Effects ». European Journal of Organic Chemistry 2006, no 7 (avril 2006) : 1755–68. http://dx.doi.org/10.1002/ejoc.200500725.

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Sandhiya, Lakshmanan, et Hendrik Zipse. « OO bond homolysis in hydrogen peroxide ». Journal of Computational Chemistry 38, no 25 (11 juillet 2017) : 2186–92. http://dx.doi.org/10.1002/jcc.24870.

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Sana, Michel, Georges Leroy, Jean-Luc Vaerman et Heinz Gunter Viehe. « The thermal isomerization of bicyclic oxazines into epoxyepimines. A preliminary theoretical study ». Canadian Journal of Chemistry 68, no 9 (1 septembre 1990) : 1625–28. http://dx.doi.org/10.1139/v90-251.

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The thermal isomerization of bicyclic oxazines 1 to epoxyepimines 2 depends on the N-substituent. BDE calculations on model systems agree with the mechanistic picture. The rate-determining step in N—O bond homolysis is facilitated by N-vinyl substituents. Keywords: oxazines, BDE, NO bond, substituent effect.
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Döpp, Dietrich. « The surprising photochemistry of sultams related to saccharin ». International Journal of Photoenergy 3, no 1 (2001) : 41–48. http://dx.doi.org/10.1155/s1110662x01000058.

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The known light induced reactions of sulfonamides and sultams are in most (but not all) cases initiated by S–N homolysis. Sulfur dioxide release may be a consequence of this primary process. In the author's laboratory three hitherto unexplored photoreactions of saccharin-derived sultams have been investigated: (i) a novel formal oxygen shift from sulfur to nitrogen generating upto now unknown cyclic N-hydroxysulfinamides; (ii) a condensative dimerization of 2,3-dihydro-1,2- benzoisothiazole 1,1-dioxide generating a new cleft molecule, and (iii) a facile allylic skeletal rearrangement of a pyrrolo-anellated dihydro- 1,2-benzoisothiazole. At least in the latter two cases an initial S–N-homolysis seems to be vital for the processes observed, whereas in the first case some ambiguity remains with respect to the first step. Scope and limitations are discussed and rationales for the conversions observed are presented, with special emphasis on structure proof by X-ray crystal structure determinations. All reactions discussed have to be treated within the wider context of current sulfonamide and sultam photochemistry.
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Li, S., et K. Lundquist. « Reactions of the β-Aryl Ether Lignin Model 1-(4-Hydroxy-3-Methoxyphenyl)-2-(2-Methoxyphenoxy)-1-Propanol on Heating in Aqueous Solution ». Holzforschung 55, no 3 (25 avril 2001) : 296–301. http://dx.doi.org/10.1515/hf.2001.049.

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Summary The reactions of the β-aryl ether lignin model 1-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)-1-propanol on heating in aqueous solution have been studied. Guaiacol, isoeugenol, vanillin, 1-(4-hydroxy-3-methoxyphenyl)-1-ethanol, 1,2-bis(4-hydroxy-3-methoxyphenyl)-1-propanol, 2-(4-hydroxy-3-methoxyphenyl)-7-methoxy-3-methyl-2,3-dihydrobenzo[b]furan, dehydrodiisoeugenol and trans-1,2-dihydrodehydroguaiaretic acid were detected in the reaction mixtures. The formation of the products can be envisioned to proceed via homolysis of an intermediate quinone methide. When 2,6-dimethoxyphenol was present in the reaction mixtures large amounts of 1-(4-hydroxy-3,5-dimethoxyphenyl)-2-(4-hydroxy-3-methoxyphenyl)-1-propanol were formed and the yields of guaiacol and isoeugenol were comparatively high. The reaction product pattern can be explained by the occurrence of radical-exchange reactions. The presence of wood meal in the reaction mixtures resulted in an increase in the yield of isoeugenol and a lowering of the yield of dehydrodiisoeugenol. The changes in yields in this case can also be explained by radical-exchange reactions. The significance of homolytic cleavage of β-aryl ether linkages in connection with the technical processing of wood is discussed.
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