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Journal articles on the topic 'Nucleophilic effects of anions'

Author: Grafiati

Published: 5 June 2025

Last updated: 1 August 2025

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1

Cervera, Maria, and Jordi Marquet. "Effects of superoxide anion generated from aromatic radical anions produced in nucleophilic aromatic photosubstitution reactions." Canadian Journal of Chemistry 76, no. 6 (1998): 966–69. http://dx.doi.org/10.1139/v98-044.

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Superoxide anion is generated from aromatic radical anions produced in nucleophilic aromatic photosubstitutions when the reactions are carried out in non-deoxygenated solutions of polar aprotic solvents. Superoxide anion thus generated displaces cyanide anion from acetonitrile and benzyl cyanide, ethoxide anion from ethyl acetate, and methanesulfenate anion from dimethyl sulfoxide. Hence, non-deoxygenated polar aprotic solvents should be avoided in nucleophilic aromatic photosubstitution reactions.Key words: superoxide, fluoride, nucleophilic aromatic photosubstitution.

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2

Attiogbe, Francis K., Wei Wang, Alastair McNeillie, and Raymond C. Francis. "The peroxymonocarbonate anions as pulp bleaching agents. Part 2. Mechanical pulp brightening and effects of metal ions." BioResources 5, no. 4 (2010): 2208–20. http://dx.doi.org/10.15376/biores.5.4.2221-2231.

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The peroxymonocarbonate mono-anion (HCO4─) is generated in solutions containing bicarbonate anions (HCO3─) and hydrogen peroxide (H2O2). The mono-anion is believed to have a pKa value of ca. 10 and as such would start dissociating to the di-anion (CO42─) at pH ca. 8. The mono-anion should demonstrate electrophilic properties, while the di-anion should be a nucleophile. Results that appear to be due to electrophilic reactions of HCO4─ were presented in Part 1 of this series for lignin model compounds (LMCs) and chemical pulps. Some evidence was also observed for nucleophilic reactions with LMCs

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3

Kuzmič, Petr, and Milan Souček. "Substituent effects in aromatic photochemistry. UV irradiation of 3,4-dimethoxybenzonitrile and 3,4-dimethoxyacetophenone in the presence of inorganic anions." Collection of Czechoslovak Chemical Communications 52, no. 4 (1987): 980–88. http://dx.doi.org/10.1135/cccc19870980.

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Ultraviolet photolysis of 3,4-dimethoxybenzonitrile (Ia) and 3,4-dimethoxyacetophenone (IIa) in the presence of the hydroxide or cyanide anion leads to nucleophilic displacement of either the para or the meta methoxy substituent. The ratio of isomeric photoproducts is dependent upon the nature of the nucleophile. Photoreactions with the OH- anion lead exclusively to the substitution at C-3. On the other hand, both isomers are formed when acetophenone IIa is irradiated in the presence of CN-, with the C-3/C-4 substitution ratio 3:2. In the case of the photocyanation of Ia, the C-4 substituted p

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4

Bunton, Clifford A., and John R. Moffatt. "Micellar effects upon substitutions by nucleophilic anions." Journal of Physical Chemistry 92, no. 10 (1988): 2896–902. http://dx.doi.org/10.1021/j100321a038.

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5

Hawker, Rebecca R., Ronald S. Haines, and Jason B. Harper. "The effect of varying the anion of an ionic liquid on the solvent effects on a nucleophilic aromatic substitution reaction." Organic & Biomolecular Chemistry 16, no. 18 (2018): 3453–63. http://dx.doi.org/10.1039/c8ob00651b.

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6

Zotti, G., G. Schiavon, and N. Comisso. "Anion effects on conductivity of isomorphous polypyrrole. Charge pinning by nucleophilic anions." Synthetic Metals 40, no. 3 (1991): 309–16. http://dx.doi.org/10.1016/0379-6779(91)92072-p.

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7

Kirby, Anthony J., José Carlos Gesser, Florian Hollfelder, Jacks P. Priebe, and Faruk Nome. "Intramolecular general acid catalysis of sulfate transfer Nucleophilic attack by oxyanions on the SO3 group." Canadian Journal of Chemistry 83, no. 9 (2005): 1629–36. http://dx.doi.org/10.1139/v05-172.

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The mechanism of hydrolysis of 8-N,N-dimethylaminonaphthyl sulfate closely resembles that of the corresponding phosphate monoester. Nucleophilic attack by water on the sulfate group of the zwitterion is catalyzed by the neighbouring dimethylammonium group, acting as a particularly efficient general acid through the intramolecular hydrogen bond. This hydrogen bond is present in both reactant and product, but is strongest in the transition state. Transfer of the sulfuryl group to oxygen nucleophiles, including water and carboxylate anions, shows steric and electrostatic effects, and a sensitivit

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8

G., Venkateswarlu, Syamala P., V. Subba Rao P., and Ramakrishna K. "Kinetics of dissociation of tris(1,10-phenanthroline)iron(II) in aqueous and reverse micellar media- catalysis of CuII, NiII and CoII ions." Journal of Indian Chemical Society Vol. 80, Feb 2003 (2003): 86–90. https://doi.org/10.5281/zenodo.5836231.

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Department of Physical and Nuclear Chemistry, School of Chemistry, Andhra University, Visakhapatnam-530 003, India <em>E-mail :</em> p_ vsrao@hotmail.com <em>Manuscript received 13 December 2001, revised 3 June 2002, accepted 13 August 2002</em> The rate of dissociation of tris(1,10-phenanthroline)iron(ll) ([Fe(phen)3]<sup>2+</sup>) is markedly increased in the presence of metal ions, Cu<sup>II</sup>, Ni<sup>II</sup> and Co<sup>II</sup> in the water pools of CTAB reverse micelles in chloroform-hexane mixture (3 : 2, v/v) compared to the aqueous medium. In both the media, the k'-(Metal ion]

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9

Afzal, D., та K. R. Fountain. "Exploration of the α-effect by substitution on hydroxylamine anions. I. Effects of alkyl- and fluoroalkylation". Canadian Journal of Chemistry 92, № 4 (2014): 346–53. http://dx.doi.org/10.1139/cjc-2013-0246.

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Many explanations for the α-effect have been suggested. Most are simple models conjecturing various sources affecting the nucleophilic behavior. This paper provides a comprehensive study of electronic effects using the single α-atom lone electron pair of substituted hydroxyl amine anions. This substituent scheme shows that the interaction of this lone pair with the negatively charged oxygen atom is an important indicator of reactivity.

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10

Toma, Mateja, Gabrijel Zubčić, Jasmina Lapić, Senka Djaković, Davor Šakić, and Valerije Vrček. "Ferrocenoyl-adenines: substituent effects on regioselective acylation." Beilstein Journal of Organic Chemistry 18 (September 19, 2022): 1270–77. http://dx.doi.org/10.3762/bjoc.18.133.

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A series of N6-substituted adenine–ferrocene conjugates was prepared and the reaction mechanism underlying the synthesis was explored. The SN2-like reaction between ferrocenoyl chloride and adenine anions is a regioselective process in which the product ratio (N7/N9-ferrocenoyl isomers) is governed by the steric property of the substituent at the N6-position. Steric effects were evaluated by using Charton (empirical) and Sterimol (computational) parameters. The bulky substituents may shield the proximal N7 region of space, which prevents the approach of an electrophile towards the N7 atom. As

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11

Benchoam, Dayana, Jonathan A. Semelak, Ernesto Cuevasanta, et al. "Acidity and nucleophilic reactivity of glutathione persulfide." Journal of Biological Chemistry 295, no. 46 (2020): 15466–81. http://dx.doi.org/10.1074/jbc.ra120.014728.

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Persulfides (RSSH/RSS−) participate in sulfur trafficking and metabolic processes, and are proposed to mediate the signaling effects of hydrogen sulfide (H2S). Despite their growing relevance, their chemical properties are poorly understood. Herein, we studied experimentally and computationally the formation, acidity, and nucleophilicity of glutathione persulfide (GSSH/GSS−), the derivative of the abundant cellular thiol glutathione (GSH). We characterized the kinetics and equilibrium of GSSH formation from glutathione disulfide and H2S. A pKa of 5.45 for GSSH was determined, which is 3.49 uni

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12

Sazonov, Petr K., and Irina P. Beletskaya. "Dualism of Ion-Pairing Effects in Nucleophilic Vinylic Substitution with Transition-Metal Carbonyl Anions." ChemPlusChem 78, no. 9 (2013): 1190–94. http://dx.doi.org/10.1002/cplu.201300171.

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13

Ofial, Armin R. "Benzhydrylium and tritylium ions: complementary probes for examining ambident nucleophiles." Pure and Applied Chemistry 87, no. 4 (2015): 341–51. http://dx.doi.org/10.1515/pac-2014-1116.

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AbstractThe linear free energy relationship log k = sN(N + E) (eq. 1), in which E is an electrophilicity, N is a nucleophilicity, and sN is a nucleophile-dependent sensitivity parameter, is a reliable tool for predicting rate constants of bimolecular electrophile-nucleophile combinations. Nucleophilicity scales that are based on eq. (1) rely on a set of structurally similar benzhydrylium ions (Ar2CH+) as reference electrophiles. As steric effects are not explicitely considered, eq. (1) cannot unrestrictedly be employed for reactions of bulky substrates. Since, on the other hand, the reactions

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14

Tee, Oswald S., Timothy A. Gadosy та Javier B. Giorgi. "Effect of β-cyclodextrin on the reaction of α-amino acid anions with p-nitrophenyl acetate and p-nitrophenyl hexanoate". Canadian Journal of Chemistry 75, № 1 (1997): 83–91. http://dx.doi.org/10.1139/v97-013.

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The effects of β-cyclodextrin (β-CD) on the kinetics of the reaction of α-amino acid anions with p-nitrophenyl acetate (pNPA) and p-nitrophenyl hexanoate (pNPH) have been investigated. Pseudo-first-order rate constants obtained with various concentrations of nucleophile and β-CD, in aqueous solution at pH 9.88, were analyzed to yield rate constants for reaction of the nucleophiles with free ester (kN) and with ester bound to β-CD (kcN). For pNPA reacting with amino acids that bind weakly to β-CD, if at all, the ratio kcN/kN is very close to one, but for amino acids that bind appreciably to β-C

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15

Tachikawa, Takashi, Ramasamy Ramaraj, Mamoru Fujitsuka, and Tetsuro Majima. "Hofmeister Effects on Electron-Transfer Reactions of 1-Pyrenesulfonic Acid Radical Cation with Nucleophilic Anions in Nafion Membranes." Journal of Physical Chemistry B 109, no. 8 (2005): 3381–86. http://dx.doi.org/10.1021/jp045606e.

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16

Popov, Anatoliy F. "Design of green microorganized systems for decontamination of ecotoxicants." Pure and Applied Chemistry 80, no. 7 (2008): 1381–97. http://dx.doi.org/10.1351/pac200880071381.

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Due to population upsurge, pesticides (derivatives of organophosphorus acids included) find widespread use in agriculture. The toxicity and long-term environmental hazard of such compounds require detailed studies on decomposition mechanisms of the pesticides and development of efficient, readily available, and inexpensive systems for their decontamination. A simple and straightforward method for the decomposition of organophosphorus compounds involves their reactions with nucleophiles. Studies on the reactivity of "normal" and α-nucleophiles toward electron-deficient centers allowed us to sta

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17

Golub, Igor E., Oleg A. Filippov, Natalia V. Belkova, Lina M. Epstein, and Elena S. Shubina. "The Reaction of Hydrogen Halides with Tetrahydroborate Anion and Hexahydro-Closo-Hexaborate Dianion." Molecules 26, no. 12 (2021): 3754. http://dx.doi.org/10.3390/molecules26123754.

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The mechanism of the consecutive halogenation of the tetrahydroborate anion [BH4]− by hydrogen halides (HX, X = F, Cl, Br) and hexahydro-closo-hexaborate dianion [B6H6]2− by HCl via electrophile-induced nucleophilic substitution (EINS) was established by ab initio DFT calculations [M06/6-311++G(d,p) and wB97XD/6-311++G(d,p)] in acetonitrile (MeCN), taking into account non-specific solvent effects (SMD model). Successive substitution of H− by X− resulted in increased electron deficiency of borohydrides and changes in the character of boron atoms from nucleophilic to highly electrophilic. This,

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18

Howell, JR, and M. Rasmussen. "Heterocyclic Ambident Nucleophiles. V. Alkylation of Benzimidazoles." Australian Journal of Chemistry 46, no. 8 (1993): 1177. http://dx.doi.org/10.1071/ch9931177.

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Alkylation of 5-substituted benzimidazole anions with a variety of primary alkyl halides in both protic and aprotic solvents showed only small regioselectivity , with a slight preference for reaction at N1 for 5-nitro and N3 for 5-methoxy systems. With 4-substituted benzimidazole anions, alkylation gave more divergent results with the N1 to N3 regioselectivity varying between 100:0 and 29:71. These alkylation patterns are interpreted as deriving from an interplay of electrostatic, thermodynamic, steric and associative control factors within the variable SN2 transition state structures involved

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19

Keaveney, Sinead T., Ronald S. Haines, and Jason B. Harper. "Developing principles for predicting ionic liquid effects on reaction outcome. The importance of the anion in controlling microscopic interactions." Organic & Biomolecular Chemistry 13, no. 12 (2015): 3771–80. http://dx.doi.org/10.1039/c4ob02482f.

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Predictable changes in the rate constant of a condensation reaction were seen as the solvent composition was varied. The cation–nucleophile interaction could be controlled in a predictable manner; activation parameters varied linearly with the H-bond acceptor ability of the anions used.

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20

Riaya, Ascencion, Montgomery T. Shaw, and Andrew Garton. "Oxidation of Elastomers in Aqueous Environments." Rubber Chemistry and Technology 67, no. 5 (1994): 775–85. http://dx.doi.org/10.5254/1.3538709.

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Abstract Crosslinked 1,4-poly butadiene (BR) and styrene-butadiene rubber (SBR) were oxidized in various ionic environments (water, neutral salt solutions, acidic and basic buffers). The acceleration of oxidation when the elastomer was immersed in neutral and basic aqueous solutions, compared to dry air, is consistent with nucleophilic attack by peroxy anions on polymer hydroperoxides to give free radicals capable of initiating further oxidation. Acidic solutions retarded oxidation, compared to air, presumably because of decomposition of hydroperoxides to nonradical products. This phenomenon i

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21

Cordier, Christopher, Li-Jie Cheng, and Alexander Brown. "From Propargylic Fluorinations to [1,3]-Rearrangements: Anion and Ligand Effects in Cu-Acetylide Chemistry." Synlett 29, no. 13 (2018): 1675–82. http://dx.doi.org/10.1055/s-0036-1591997.

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Metal-catalyzed reactions of propargylic substrates have been widely studied. Of this reaction class, Cu-catalyzed methods have received much attention within the past decade, with Cu-allenylidenes being proposed as key reactive intermediates. This Synpacts article will outline our development of a nucleophilic fluorination protocol of propargylic electrophiles using copper catalysis. Following an analysis of the importance of anion and ligand effects, this study led us to the unexpected discovery of a formal [1,3]-rearrangement of O-propargylic alkoxypyridine derivatives that was later render

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22

Zachernyuk, Alexander B. "Polysilazaoxanes and adhesive compositions based on them." Butlerov Communications 62, no. 4 (2020): 19–25. http://dx.doi.org/10.37952/roi-jbc-01/20-62-4-19.

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The polymer formation proceeding with the participation of cardosilazaoxane organosilicon oligomers are considered. By the interaction of cardocyclic silazaoxanes with organosiloxane diols, new types of organosilicon oligomers are synthesized. They are capable to form elastic spatial-netted structures due to polymerization processes with the discovery of cyclic siloxane fragments without isolation of low molecular weight by-products. The influence of temperature and the silazaoxane: diol ratio on the nature of the products formed is studied. It was established that at 120-130 °C soluble oligom

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23

Balakrishnan, Vimal K., Julian M. Dust, Gary W. vanLoon, and Erwin Buncel. "Catalytic pathways in the ethanolysis of fenitrothion, an organophosphorothioate pesticide. A dichotomy in the behaviour of crown/cryptand cation complexing agents." Canadian Journal of Chemistry 79, no. 2 (2001): 157–73. http://dx.doi.org/10.1139/v01-006.

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The rates of displacement of 3-methyl-4-nitrophenoxide ion from the pesticide, fenitrothion, by alkali metal ethoxides in anhydrous ethanol were followed spectrophotometrically. Through product analysis experiments, which included 31P NMR and GC-MS, as well as spectrophotometric analysis, three reaction pathways were identified: nucleophilic attack at the phosphorus centre, attack at the aliphatic carbon, and a minor SNAr route ([Formula: see text]7%). Furthermore, a consecutive process was found to occur on the product of attack at the phosphorus centre. For purposes of kinetic treatment, the

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24

Tureček, František. "Stereochemistry of organic ions in the gas phase: A review." Collection of Czechoslovak Chemical Communications 52, no. 8 (1987): 1928–84. http://dx.doi.org/10.1135/cccc19871928.

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The stereochemistry of organic ions in the gas phase can be regarded from two different points of view: (i) stereoselectivity in ion formation and (ii) stereospecifity of ion fragmentations. Fast ionization by electron or photon impact shows little stereoselection. Differences in the ionization energies and cross sections between stereoisomers are generally small, save for a few exceptions. Proton or larger ion transfer, as employed in chemical ionization mass spectrometry, gives more possibilities for stereoselection. Bi- or polyfunctional molecules can capture the proton in a hydrogen-bond s

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25

Tee, Oswald S., and Michael J. Boyd. "Aminolysis of naphthyl acetates catalyzed by cyclodextrins." Canadian Journal of Chemistry 77, no. 5-6 (1999): 950–59. http://dx.doi.org/10.1139/v99-086.

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The effects of cyclodextrins (CDs) on the rate of nucleophilic attack on 1- and 2-naphthyl acetates (1-NA and 2-NA) in aqueous solution have been investigated. Analysis of the variation of the pseudo-first-order rate constants with [nucleophile] and [CD] affords rate constants for reaction of the nucleophiles with free ester (kN) and with ester bound to the CD (kcN). The reaction of 1-NA and 2-NA with the trifluoroethoxide anion is slowed down by β-CD as the ratios kcN/kN are 0.11 and 0.30, respectively. For reaction with the anion of 2-mercaptoethanol in the presence of α-CD, β-CD, "hydroxypr

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26

Wang, Weihua, Yuhua Wang, Wenling Feng, Wenliang Wang, and Ping Li. "Theoretical Investigations on the Reactivity of Hydrogen Peroxide toward 2,3,7,8-Tetrachlorodibenzo-p-dioxin." Molecules 23, no. 11 (2018): 2826. http://dx.doi.org/10.3390/molecules23112826.

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Acquiring full knowledge of the reactivity of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) is crucial for the better understanding of the transformation and degradation of TCDD-like dioxins in the environment. To clarify the reactivity of the organic hydroperoxides toward TCDD, in this study, the reactions between the neutral/anion of the hydrogen peroxide (H2O2) and TCDD have been systematically investigated theoretically. It was found that the neutral H2O2 is relatively difficult to react with TCDD compared with its anion, exhibiting the pH dependence of the title reaction. As for the anion of

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27

Oh, Young-Ho, Dong Wook Kim, and Sungyul Lee. "Ionic Liquids as Organocatalysts for Nucleophilic Fluorination: Concepts and Perspectives." Molecules 27, no. 17 (2022): 5702. http://dx.doi.org/10.3390/molecules27175702.

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Besides their extremely useful properties as solvent, ionic liquids (ILs) are now considered to be highly instructive tools for enhancing the rates of chemical reactions. The ionic nature of the IL anion and cation seems to be the origin of this fascinating function of ILs as organocatalyst/promoter through their strong Coulombic forces on other ionic species in the reaction and also through the formation of hydrogen bonds with various functional groups in substrates. It is now possible to tailor-make ILs for specific purposes as solvent/promoters in a variety of situations by carefully monito

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28

Augusti, Rodinei, Xubin Zheng, M. Turowski, and R. Graham Cooks. "Kinetic Isotope and Collision Energy Effects in the Dissociation of Chloride and Bromide Adducts of Aliphatic Alcohols, Benzaldehyde, and 2,4-Pentanedione." Australian Journal of Chemistry 56, no. 5 (2003): 415. http://dx.doi.org/10.1071/ch02245.

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A tandem-in-space triple quadrupole mass spectrometer was used to measure kinetic isotopic effects (KIEs) for the dissociation of chloride and bromide adducts of several compounds that bind halide anions via either hydrogen bonds or by nucleophilic attachment. Two isotopomers of each adduct were simultaneously mass-selected in the first quadrupole and dissociated by collision with argon in the second quadrupole. The KIEs were measured by comparing the extents of dissociation of the lighter versus the heavier isotopomeric adducts. In most cases, lower collision energies and multiple collision c

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29

Haqghu, M., M. Irani, and M. R. Gholami. "Theoretical Study of Kinetics and Mechanism of Reactions of Hydroxylamine and Amineoxide Anion with Methyl Iodide in Gas and Aqueous Phases." Progress in Reaction Kinetics and Mechanism 32, no. 1 (2007): 29–50. http://dx.doi.org/10.3184/146867807x227462.

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The kinetics and mechanism of the reactions of hydroxylamine and aminoxide anion with methyl iodide were studied with ab initio calculations, Monte-Carlo and QM/MM simulations in gas and aqueous phases. Geometrical parameters and charge calculations show that these reactions proceed through the SN2 (bimolecular nucleophilic displacement) mechanism only. The solvent effects on these reactions were studied by inserting water molecules in reaction media, Onsager model, Monte-Carlo and QM/MM simulations. Activation parameters indicate the expected variation in activation energy and rate coefficien

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30

Afanas'ev, Igor. "Reactive Oxygen Species and Age-Related Genes p66Shc, Sirtuin, FoxO3 and Klotho in Senescence." Oxidative Medicine and Cellular Longevity 3, no. 2 (2010): 77–85. http://dx.doi.org/10.4161/oxim.3.2.11050.

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Reactive oxygen species (ROS) superoxide and hydrogen peroxide perform important signaling functions in many physiological and pathophysiological processes. Cell senescence and organismal age are not exemptions. Aging-regulating genesp66shc, Sirtuin, FOXO3aandKlothoare new important factors which are stimulated by ROS signaling. It has been shown that ROS participate in initiation and prolongation of gene-dependent aging development. ROS also participate in the activation of protein kinases Akt/PKB and extracellular signal-regulated kinase ERK, which by themselves or through gene activation st

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Reeds, Jonathan P., Adrian C. Whitwood, Mark P. Healy, and Ian J. S. Fairlamb. "Remarkable anion effects uncovered in the development of a Au(iii)-catalyzed tandem nucleophilic substitution–1,5-enyne cycloisomerization process." Chemical Communications 46, no. 12 (2010): 2046. http://dx.doi.org/10.1039/b925919h.

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Acharjee, Nivedita. "Solvent effects on cycloaddition reactions of potent spin-trapping probe N-tert-butylmethanimine N-oxide: A DFT study." Journal of Theoretical and Computational Chemistry 17, no. 04 (2018): 1850027. http://dx.doi.org/10.1142/s021963361850027x.

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[Formula: see text]-tert-butylmethanimine [Formula: see text]-oxide is a potent spin-trapping probe for biologically important radicals, and this nitrone undergoes complete regioselective cycloadditions to less electron-deficient monosubstituted olefins. In the present study, solvent effects on the cycloaddition of this nitrone to styrene have been theoretically studied in terms of the global properties of the reactants, electrophilic and nucleophilic Parr function analysis and the activation and reaction energies of located transition states and products. Formation energies of optimized radic

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Wu, Ivy, Mei-Chen Kuo, Kevin Dunn, et al. "Using a Tunable Triblock Cationic Polymer to Unravel Performance and Durability Effects in Anion Exchange Membrane Based Electrolysis." ECS Meeting Abstracts MA2023-01, no. 36 (2023): 2030. http://dx.doi.org/10.1149/ma2023-01362030mtgabs.

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The use of anion exchange membranes (AEMs) as the polymer electrolyte membrane and related cationic polymers as ionomers in the electrodes of water splitting electrolyzers could lead to significant advantages including the elimination of precious metal electrocatalysts. Because oxygenated radicals in base have a very much lower half life than in acid these materials can be based on hydrocarbon backbones. This leads to an enormous possible variation in polymer chemistry and, while exciting from the point of view of the creation of new polymer chemistries, has led to a lack of detail in determin

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Guk, Dmitry A., Karina R. Gibadullina, Roman O. Burlutskiy, et al. "New Titanocene (IV) Dicarboxylates with Potential Cytotoxicity: Synthesis, Structure, Stability and Electrochemistry." International Journal of Molecular Sciences 24, no. 4 (2023): 3340. http://dx.doi.org/10.3390/ijms24043340.

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The search for new anticancer drugs based on biogenic metals, which have weaker side effects compared to platinum-based drugs, remains an urgent task in medicinal chemistry. Titanocene dichloride, a coordination compound of fully biocompatible titanium, has failed in pre-clinical trials but continues to attract the attention of researchers as a structural framework for the development of new cytotoxic compounds. In this study, a series of titanocene (IV) carboxylate complexes, both new and those known from the literature, was synthesized, and their structures were confirmed by a complex of phy

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35

Turovskaya, M. K., T. M. Prokopyeva, T. S. Gaidash та V. A. Mikhailov. "α-nucleophiles as the basis of organized supernucleophilic microheterogeneous systems for the destruction of rganophosphorus compounds". Vestnik NovSU, № 3 (2023): 374–82. http://dx.doi.org/10.34680/2076-8052.2023.3(132).374-382.

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Peroxyhydrolysis of 4-nitrophenyl esters of phosphoric and phosphonic acids has been studied in organized microheterogeneous systems based on dimeric cationic imidazole-containing surfactants (AlkIm+-(CH2)m-Im+Alk ∙ 2Br- , m = 2,3,4, Alk = C12H25, C14H29). Micellar effects of the surfactants (at pH = const and [surfactant]0 = const) reach ~ 10–100 times. Physicochemical parameters of the peroxyhydrolysis process (such as substrate binding constants, hydroperoxide anion nucleophilicity in micellar pseudophase) are described in terms of the pseudophase distribution model. Observed rate enhanceme

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36

Hartl, Frantiek. "Nucleophilic attack at the five-coordinate anion [Mn(CO)3(3,5-di-tert-butyl-catecholate)]− controlled by electronic and steric effects." Inorganica Chimica Acta 268, no. 1 (1998): 1–11. http://dx.doi.org/10.1016/s0020-1693(97)05627-2.

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Reeds, Jonathan P., Adrian C. Whitwood, Mark P. Healy, and Ian J. S. Fairlamb. "ChemInform Abstract: Remarkable Anion Effects Uncovered in the Development of a Au(III)-Catalyzed Tandem Nucleophilic Substitution-1,5-Enyne Cycloisomerization Process." ChemInform 41, no. 30 (2010): no. http://dx.doi.org/10.1002/chin.201030054.

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Berven, Leise A., David Dolphin, and Stephen G. Withers. "The base-catalysed anomerization of dinitrophenyl glycosides: evidence for a novel reaction mechanism." Canadian Journal of Chemistry 68, no. 10 (1990): 1859–66. http://dx.doi.org/10.1139/v90-288.

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The mechanism of base-catalysed anomerization of per-O-acetylated 2,4-dinitrophenyl-β-D-glucopyranoside in dimethylsulfoxide has been investigated using a variety of techniques. A mechanism involving proton abstraction at C-1 was eliminated by the absence of proton exchange at that center and the measurement of a secondary deuterium kinetic isotope effect for the 1-deuterio substrate. A mechanism involving phenolate departure and recombination is rendered unlikely on the basis of remote substituent effects on the reaction rate and by the absence of any exchange of the phenyl moiety with added

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39

Campagnolo, Filippo, Eleonora Aneggi, Walter Baratta, Talha Munir, and Daniele Zuccaccia. "Diffusion Nuclear Magnetic Resonance Measurements on Cationic Gold (I) Complexes in Catalytic Conditions: Counterion and Solvent Effects." Molecules 29, no. 13 (2024): 3018. http://dx.doi.org/10.3390/molecules29133018.

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The amount of free ions, ion pairs, and higher aggregate of the possible species present in a solution during the gold(I)-catalyzed alkoxylation of unsaturated hydrocarbon, i.e., ISIP (inner sphere ion pair) [(NHC)AuX] and OSIP (outer sphere ion pairs) [(NHC)Au(TME)X] [NHC 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene; TME = tetramethylethylene (2,3-bis methyl-butene); X− = Cl−, BF4−, OTf−; and OTs− BArF4− (ArF = 3,5-(CF3)2C6H3)], has been determined. The 1H and 19F DOSY NMR measurements conducted in catalytic conditions indicate that the dissociation degree (α) of the equilibrium ion pai

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Bonnans-Plaisance, Chantal, and Jean-Claude Gressier. "Nucleophilic substitution by benzodithioate anions." Journal of Chemical Education 65, no. 1 (1988): 93. http://dx.doi.org/10.1021/ed065p93.

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Novikov, Vitaly Yu, Svetlana R. Derkach, Irina N. Konovalova, Natalya V. Dolgopyatova, and Yulya A. Kuchina. "Mechanism of Heterogeneous Alkaline Deacetylation of Chitin: A Review." Polymers 15, no. 7 (2023): 1729. http://dx.doi.org/10.3390/polym15071729.

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This review provides an analysis of experimental results on the study of alkaline heterogeneous deacetylation of chitin obtained by the authors and also published in the literature. A detailed analysis of the reaction kinetics was carried out considering the influence of numerous factors: reaction reversibility, crystallinity and porosity of chitin, changes in chitin morphology during washing, alkali concentration, diffusion of hydroxide ions, and hydration of reacting particles. A mechanism for the chitin deacetylation reaction is proposed, taking into account its kinetic features in which th

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42

Popov, Anatolii, Illia Kapitanov, Anna Serdyuk та Aleksandr Sumeiko. "REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS (Part 2)". Ukrainian Chemistry Journal 86, № 8 (2020): 77–100. http://dx.doi.org/10.33609/2708-129x.86.8.2020.77-100.

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The review analyzes issues related to the reactivity of nucleophiles and the manifestation of the α-effect in substitution processes at electron-deficient centers. The fundamental aspects of this phenomenon, as well as the possibilities and prospects of using α-nucleophiles in systems for the highly efficient degradation of substrates - ecotoxicants of various natures, are discussed. In the first part of the review such aspects were observed: inorganic α-nucleophiles as the most effective class of reagents for the decomposition of organic phosphorus compounds, hydroxylamine, its N-alkyl deriva

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Huang, Shan, and Hanying Zhao. "Thiol‐dithioester reaction: An approach to the end‐group removal and end‐functionalization of RAFT‐synthesized polymers." Journal of Polymer Science 62, no. 24 (2024): 5598–608. https://doi.org/10.1002/pol.20240501.

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AbstractReversible addition−fragmentation chain transfer (RAFT) polymerization has been one of the most versatile methods in the synthesis of well‐defined polymers. The stability of the thiocarbonylthio chain transfer agents (CTAs) in the polymerization and the removal of CTAs after the polymerization are the two great concerns for the applications of RAFT polymerization. In this research, thiol‐dithioester reaction under the catalysis of triethylamine (TEA) is studied. In a model reaction, thiolate anion has nucleophilic addition reaction with dithioester compound, resulting in the synthesis

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Breugst, Martin, Takahiro Tokuyasu, and Herbert Mayr. "Nucleophilic Reactivities of Imide and Amide Anions." Journal of Organic Chemistry 75, no. 15 (2010): 5250–58. http://dx.doi.org/10.1021/jo1009883.

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Stoin, Uri, Zach Barnea, and Yoel Sasson. "New technology for post-combustion abatement of carbon dioxide via an in situ generated superoxide anion-radical." RSC Adv. 4, no. 69 (2014): 36544–52. http://dx.doi.org/10.1039/c4ra03844d.

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Christoffers, Jens, and David Kieslich. "Cyanide Anions as Nucleophilic Catalysts in Organic Synthesis." Synthesis 53, no. 19 (2021): 3485–96. http://dx.doi.org/10.1055/a-1499-8943.

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AbstractThe nucleophilic addition of a cyanide anion to a carbonyl group is the basis for several cyanide-catalyzed organic reactions, which are summarized in this review. Since cyanide is also a good leaving group, it is an excellent catalyst for transacylation reactions. As an electron-withdrawing group, it also stabilizes a negative charge in its α-position, thus allowing the umpolung of aldehydes to formyl anion equivalents. The two leading examples are the benzoin condensation and the Michael–Stetter reaction furnishing α-hydroxy ketones and 1,4-dicarbonyl compounds, which are both cataly

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MORI, Yuji. "Reaction of Oxiranyl Anions as a Nucleophilic Epoxide." Journal of Synthetic Organic Chemistry, Japan 55, no. 3 (1997): 176–85. http://dx.doi.org/10.5059/yukigoseikyokaishi.55.176.

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Yamashita, Makoto. "Creation of Nucleophilic Boryl Anions and Their Properties." Bulletin of the Chemical Society of Japan 84, no. 10 (2011): 983–99. http://dx.doi.org/10.1246/bcsj.20110123.

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Puente, Ángel, Armin R. Ofial, and Herbert Mayr. "Nucleophilic Reactivities of Bis-Acceptor-Substituted Benzyl Anions." European Journal of Organic Chemistry 2017, no. 8 (2017): 1196–202. http://dx.doi.org/10.1002/ejoc.201601513.

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Cognigni, Alice, Peter Gaertner, Ronald Zirbs, et al. "Surface-active ionic liquids in micellar catalysis: impact of anion selection on reaction rates in nucleophilic substitutions." Physical Chemistry Chemical Physics 18, no. 19 (2016): 13375–84. http://dx.doi.org/10.1039/c6cp00493h.

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