Thermodynamics of complex formation of silver(I) with N-donor ligands in non-aqueous solvents

Melchior, Andrea; Tolazzi, Marilena; Polese, Pierluigi; Zanonato, Pier Luigi

doi:10.1007/s10973-017-6289-1

Cited by 12 publications

(6 citation statements)

References 59 publications

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“…Silver(I) ions are known to coordinate various types of ligands such as amines, amides, and olefins. − Imidazole-based ligands can coordinate to the silver(I) ion to form linear monocoordinated (Ag + L) and dicoordinated (Ag + L 2 ) silver(I) ion complexes , and have been utilized to modulate the complexation of analytes possessing π-bonds . To investigate the effect of ligand-coordinated silver(I) ion pseudophases on analyte partitioning, monocoordinated ([Ag + (DMIM)][NTf 2 – ]) and dicoordinated ([Ag + (MIM)(DMIM)][NTf 2 – ]) silver(I) salts were synthesized, as shown in Figure and used to prepare stationary phases containing varying amounts of these silver(I) salts dissolved in the [C 10 MIM + ][NTf 2 – ] IL (see Table ).…”

Section: Resultsmentioning

confidence: 99%

Using a Chromatographic Pseudophase Model To Elucidate the Mechanism of Olefin Separation by Silver(I) Ions in Ionic Liquids

Eor

Anderson

2021

Anal. Chem.

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Silver(I) ions undergo selective olefin complexation and have been utilized in various olefin/paraffin separation techniques such as argentation chromatography and facilitated transport membranes. Ionic liquids (ILs) are solvents known for their low vapor pressure, high thermal stability, low melting points, and ability to promote a favorable solvation environment for silver(I) ion−olefin interactions. To develop highly selective separation systems, a fundamental understanding of analyte partitioning to the stationary phase and the thermodynamic driving forces behind solvation is required. In this study, a chromatographic model treating silver(I) ions as a pseudophase is constructed and employed for the first time to investigate the olefin separation mechanism in silver(I) salt/IL mixtures. Stationary phases containing varying amounts of noncoordinated silver(I) salt− ]) IL are utilized to determine the partition coefficients of various analytes including alkanes, alkenes, alkynes, aromatics, aldehyde, esters, and ketones. As ligand coordination to silver(I) ions is known to lower its olefin complexation capability, this study also examines two different types of coordinated silver(I) ion pseudophases, namely, monocoordinated silver(I) salt ([Ag + (1-decyl-2-methylimidazole, DMIM)]-[NTf 2 − ]) and dicoordinated silver(I) salt ([Ag + (1-methylimidazole, MIM)(DMIM)][NTf 2 − ]). The extent of olefin partitioning to the coordinated silver(I) ion pseudophases over the carrier gas and IL decreased by up to two orders of magnitude. Values for enthalpy, entropy, and free energy of solvation were determined for the three silver(I) ion-containing systems. Olefin retention was observed to be enthalpically dominated, while ligand coordination to the silver(I) ion pseudophase resulted in variations for both enthalpic and entropic contributions to the free energy of solvation. The developed model can be used to study chemical changes that occur in silver(I) ions over time as well as identify optimal silver(I) salt/IL mixtures that yield high olefin selectivity.

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Section: Resultsmentioning

confidence: 99%

Using a Chromatographic Pseudophase Model To Elucidate the Mechanism of Olefin Separation by Silver(I) Ions in Ionic Liquids

Eor

Anderson

2021

Anal. Chem.

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“…The pyridine-silver complexes are widely used in science and industry: as catalysts, oxidants and explosives [1][2][3][4][5]. Some of the numerous possible compounds of this class can be synthesized easily, and some of the properties of a few of them have been studied [6,7].…”

Section: Introductionmentioning

confidence: 99%

Thermal and spectroscopic studies on a double-salt-type pyridine–silver perchlorate complex having κ1-O coordinated perchlorate ions

Holló

Petruševski

Kovács

et al. 2019

J Therm Anal Calorim

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A simple synthetic method was developed to prepare 4[Agpy 2 ClO 4 ]Á[Agpy 4 ]ClO 4 in a low-temperature decomposition process of [Agpy 4 ]ClO 4 . A detailed IR, Raman and far-IR study including factor group analysis has been performed, and the assignation of bands is given. The compound decomposes quickly with a multistep ligand loss process with the formation of [Agpy 2 ]ClO 4 and AgClO 4 intermediates and AgCl as an end product around * 85, * 350 and 450°C, respectively. During the first decomposition step, a small fraction of the ligands is lost in a redox reaction: perchlorate oxidizes the pyridine, forming carbon, carbon dioxide, water and NO, while it itself is reduced into AgCl. In the next step, when AgClO 4 forms after complete ligand loss and reacts with the carbon formed in the degradation of pyridine at lower temperatures and produces NO, CO 2 and H 2 O. This reaction becomes possible because the AgCl formed in the redox reactions makes a eutectic melt with AgClO 4 in situ, which is a favorable medium for the carbon oxidation reaction. AgCl is known to reduce the temperature of decomposition of AgClO 4 , in which process forms AgCl as well as O 2 and so is an autocatalytic process. The loss and degradation of pyridine ligand are endothermic; the redox reactions including carbon oxidation and AgClO 4 decomposition into AgCl and O 2 are exothermic. The amount of absorbed/evolved heats corresponding to these processes was determined by DSC both under N 2 and O 2 atmospheres. Keywords Pyridine-silver complexes Á Perchlorates Á Quasi-intramolecular solid-phase redox reaction Á Evolved gas analysis Á DSC Electronic supplementary material The online version of this article (

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“…For the Ag + /terpy system seven different models have been checked to fit the experimental data, taking into account different combination of AgiLj mononuclear and polynuclear species (i = 1, 2; j =1, 2, 3), as this ions is known to form also polynuclear species in non-aqueous solutions [8,[38][39][40].…”

Section: Complexes In Non-aqueous Solutionmentioning

confidence: 99%

“…As described above, some metal ions have the ability to form multinuclear complexes of MiLj in solution [21,40,42,43]. Such species can be of difficult identification from calorimetric data alone and often require the simultaneous fitting of several titrations with different concentrations of the metal ion [21,38]. To check the performance of the analysis made by cEST, calorimetric data where the metal is titrated with the ligand were simulated on the basis of a model including either the ML species alone or in co-presence with the M2L2.…”

Section: Multinuclear Complexesmentioning

confidence: 99%

cEST: a flexible tool for calorimetric data analysis

Polese

Tolazzi

Melchior

2018

J Therm Anal Calorim

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A new MS-Excel utility based on the EST speciation tool (cEST) specifically designed to be applied to the analysis of calorimetric data is presented in this work. The cEST utility is able to fit calorimetric data with species of arbitrary stoichiometry and also automatically provides a complex statistical analysis of data fitting. This latter aspect is often very useful to discriminate the goodness of fit for different models. As cEST runs under MS-Excel, it is flexible in its implementation and allows a straightforward data import and graphing. Furthermore, it is open source and can be used within both Windows and MacOS operating systems. The applicability of cEST is tested towards data of different origin: experimental data, where the complex formation between Ag + , Co 2+ and Cd 2+ ions and terpyridine in anhydrous DMSO is studied, and simulated ITC points for biomolecular interactions with either two or three-binding sites. In the case of metal complex formation, the combination with regression statistics allows the choice of the best model among those for which convergence is achieved. In this case, the Akaike Information Criterion (AICc) is employed for selecting the model for the metal-terpyridine speciation. Our analysis, based on independent calorimetric data, provides models and thermodynamic parameters which are in good agreement with those of the original works obtained by combining different complementary techniques. Also, in all the examined cases, the results obtained for the biomolecular interactions provide thermodynamic parameters which are strictly in line with the published results.

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Thermodynamics of complex formation of silver(I) with N-donor ligands in non-aqueous solvents

Cited by 12 publications

References 59 publications

Using a Chromatographic Pseudophase Model To Elucidate the Mechanism of Olefin Separation by Silver(I) Ions in Ionic Liquids

Using a Chromatographic Pseudophase Model To Elucidate the Mechanism of Olefin Separation by Silver(I) Ions in Ionic Liquids

Thermal and spectroscopic studies on a double-salt-type pyridine–silver perchlorate complex having κ1-O coordinated perchlorate ions

cEST: a flexible tool for calorimetric data analysis

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