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Aquation

About: Aquation is a research topic. Over the lifetime, 1443 publications have been published within this topic receiving 17507 citations.


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Journal ArticleDOI
TL;DR: The steric course for Hg2+ and NO+ promoted aquation of some bis(ethylenediamine)cobalt(III) cations has been accurately determined at 23°C as discussed by the authors.

12 citations

Journal ArticleDOI
TL;DR: In this paper, a stochastic ratio of Δ[IrCl6]2−/Δ[NH2OH] was obtained for the oxidation of hydroxylammonium ion in acetic acid-acetate buffer solutions, studied by stopped flow.
Abstract: The oxidation of hydroxylammonium ion by [IrCl6]2− ion in acetic acid – acetate buffer solutions, studied by stopped flow, has the stoichiometric ratio Δ[IrCl6]2−/Δ[NH2OH] = 1. The oxidation involves the species [IrCl6]2− and NH3OH+ although spectral analysis of the spent reaction mixture indicates [IrCl5(OH2)]2− to be the main product (almost to the extent of 80%). This anomaly arises because of the aquation of the reduced product [IrCl6]3−. The rate is retarded both by H+ and Cl− ions and the plots of against respective concentrations are linear. The proposed mechanism is given by reactions [i]–[v].The values of the rate constants at 25 °C are as follows: k1 = 147 dm3 mol−1 s−1 and 102ketKia = 2.8 s−1. The related activation parameters are , and,, and and , respectively. The value of Kipd is 2.91 ± 0.03 mol dm−3 and that of Kipa (= 1/Kipd) is 0.344 ± 0.004 dm3 mol−1; both values are almost independent of temperature.

12 citations

Journal ArticleDOI
TL;DR: In this article, the metal-promoted reaction of the ligand carbonyl group with water or alcohols was investigated and a new compound of cobalt(II), cobalt (III), iron(II) and iron(III) with di-(2-pyridyl)ketone (pyCOpy) was reported.

12 citations

Journal ArticleDOI
TL;DR: Mecanisme de l'hydrolyse des complexes as mentioned in this paper : Les vitesses relatives des reactions dependent de la taille du cycle forme par attaque du thiol
Abstract: Mecanisme de l'hydrolyse des complexes. Les vitesses relatives des reactions dependent de la taille du cycle forme par attaque du thiol

11 citations

Journal ArticleDOI
TL;DR: The reaction of trans-[Co(salen)(OH2)(SO3-S)] with SO2 yields trans-(Co,salen)2(OH2)-SO3S]-− (S-bonded isomer) for which the rate and activation parameters at 25°C (I,pk,pK,p,p−1.1,p −0.1 at 25−°C, I,p,pK,p,1,P,1 −0.,pK −1, pK −0,p
Abstract: The reaction of trans-[Co(salen)(OH2)OH] with SO2 yields trans-[Co(salen)(OH2)(SO3-S)]− (S-bonded isomer) for which the rate and activation parameters at 25 °C (I = 0.3 mol dm−3) are kSO2 = (5.9 ± 0.1) × 1010 dm3 mol−1 s−1, ΔH‡ = 66 ± 4 kJ mol−1 and ΔS‡ = 183 ± 14 J K−1 mol−1. One possibility for the SIV substitution is that Co–S bond formation is concerted with Co–O bond breaking. An alternative mechanism, involving a fast equilibrium between SO2 and trans-[Co(salen)(OH2)OH] forming an O-bonded sulfito species which then undergoes sulfite ligand linkage isomerisation, is also possible. An estimated value of the isomerisation rate constant for the trans-[Co(salen)(OH2)(OSO2H)] at 25 °C is ca. 106 s−1. The trans-[Co(salen)(OH2)(SO3-S)]− (pK = 10.1 ± 0.1 at 25 °C, I = 0.3 mol dm−3) undergoes acid catalysed aquation to yield the parent diaqua complex and SIV with kH = 29.5 ± 1.1 dm3 mol−1 s−1, ΔH‡ = 72 ± 3 kJ mol−1, ΔS‡ = 24 ± 9 J K−1 mol−1 at 25 °C (I = 0.3 mol dm−3). Steady state photolysis (254 nm) of trans-[Co(salen)(OH2)(SO3-S)]− resulted in the reduction of CoIII. The redox rate constant and ϕ(Co2+) decreased with increasing pH. Attempts to detect an O-bonded sulfito complex as a transient in the conventional flash photolysis of this aqua-sulfito complex proved unsuccessful. The aqua ligand replacement reactions of trans-[Co(salen)(OH2/OH)(OH2)]+/0 with imidazole and that of the corresponding aqua-sulfito complex with N3−, NCS−, imidazole, and SIV in a large excess of the entering ligands have been studied at 25 °C. A comparison of the rate constants with the analogous data for trans-[Co(AA)2(OH2)(SO3-S)]+ (AA = 1,2-diaminoethane; 1,3-diaminopropane) clearly shows that the kinetic trans-effect of the S-bonded sulfite is substantially attenuated in trans-[Co(salen)(OH2)(SO3-S)]−.

11 citations

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Performance
Metrics
No. of papers in the topic in previous years
YearPapers
20232
20226
202111
202010
201914
20187