Thermodynamics of ion pairs in mixed solvents. I. The standard association constant of the ion pair [ MgSO4]oin { 0.03226 CO(NH2)2+ 0.96774 H2O}

2001 ◽  
Vol 33 (2) ◽  
pp. 179-188 ◽  
Author(s):  
Jia-Zhen Yang ◽  
Ru-Bo Zhang ◽  
Hong Liu ◽  
Jie Wang
Keyword(s):  
Association Constant ◽  
Ion Pairs ◽  
Mixed Solvents ◽  
Ion Pair

Application of 59Co NMR to the investigation of interactions between cobalt sepulchrate and various counterions

1991 ◽  
Vol 69 (3) ◽  
pp. 567-569 ◽  
Author(s):  
João Sotomayor ◽  
Helena Santos ◽  
Fernando Pina
Keyword(s):  
Quantum Yield ◽  
Association Constant ◽  
Chemical Shifts ◽  
Cobalt Complex ◽  
Ion Pairs ◽  
Formation Constants ◽  
Ion Pair ◽  
Association Constants ◽  
Quantum Yields ◽  
True Quantum

Association constants for the ion pairs formed between [Co(Sep)]3+ and the anions fluoride, chloride, bromide, iodide, perchlorate, and oxalate were obtained from the chemical shifts of the 59Co resonance that occur upon addition of such anions to solutions of the cobalt complex. The usefulness of 59Co NMR to obtain formation constants, in order to calculate the "true" quantum yields for the ion pairs, is discussed. Key words: association constant, cobalt sepulchrate, ion pair, 59Co NMR, quantum yield.

Stereospecific 1,3-H Transfer of Indenols Proceeds via Persistent Ion-Pairs Anchored By NH···Pi Interactions

2018 ◽  
Author(s):  
David Ascough ◽  
Fernanda Duarte ◽  
Robert Paton
Keyword(s):  
Computational Analysis ◽  
Ion Pairs ◽  
Ion Pair ◽  
Hydrogen Atom Transfer ◽  
Polar Solvents ◽  
Chirality Transfer ◽  
Activation Barriers ◽  
Sense And Avoid ◽  
Phase Dynamics ◽  
Pi Interactions

The base-catalyzed rearrangement of arylindenols is a rare example of a suprafacial [1,3]-hydrogen atom transfer. The mechanism has been proposed to proceed via sequential [1,5]-sigmatropic shifts, which occur in a selective sense and avoid an achiral intermediate. A computational analysis using quantum chemistry casts serious doubt on these suggestions: these pathways have enormous activation barriers and in constrast to what is observed experimentally, they overwhelmingly favor a racemic product. Instead we propose that a suprafacial [1,3]-prototopic shift occurs in a two-step deprotonation/reprotonation sequence. This mechanism is favored by 15 kcal mol<sup>-1</sup> over that previously proposed. Most importantly, this is also consistent with stereospecificity since reprotonation occurs rapidly on the same p-face. We have used explicitly-solvated molecular dynamics studies to study the persistence and condensed-phase dynamics of the intermediate ion-pair formed in this reaction. Chirality transfer is the result of a particularly resilient contact ion-pair, held together by electrostatic attraction and a critical NH···p interaction which ensures that this species has an appreciable lifetime even in polar solvents such as DMSO and MeOH.

scholarly journals Tripodal, Squaramide-Based Ion Pair Receptor for Effective Extraction of Sulfate Salt

Molecules ◽  
2021 ◽  
Vol 26 (9) ◽  
pp. 2751
Author(s):  
Damian Jagleniec ◽  
Marcin Wilczek ◽  
Jan Romański
Keyword(s):  
Ion Pairs ◽  
Binding Mode ◽  
Selective Extraction ◽  
Ion Pair ◽  
Hofmeister Series ◽  
Sulfate Salt ◽  
Lower Affinity ◽  
High Affinity ◽  
Binding Domains ◽  
Hydrated Sulfate

Combining three features—the high affinity of squaramides toward anions, cooperation in ion pair binding and preorganization of the binding domains in the tripodal platform—led to the effective receptor 2. The lack of at least one of these key elements in the structures of reference receptors 3 and 4 caused a lower affinity towards ion pairs. Receptor 2 was found to form an intramolecular network in wet chloroform, which changed into inorganic–organic associates after contact with ions and allowed salts to be extracted from an aqueous to an organic phase. The disparity in the binding mode of 2 with sulfates and with other monovalent anions led to the selective extraction of extremely hydrated sulfate anions in the presence of more lipophilic salts, thus overcoming the Hofmeister series.

Thermodynamics of Protonation and Sodium Binding of Sulfate in Concentrated NaCl and CsCl Solutions Studied by Raman Spectroscopy

2000 ◽  
Vol 53 (5) ◽  
pp. 363 ◽  
Author(s):  
Steven Kratsis ◽  
Glenn Hefter ◽  
Peter M. May ◽  
Pal Sipos
Keyword(s):  
Raman Spectroscopy ◽  
Excellent Agreement ◽  
Thermodynamic Data ◽  
Association Constant ◽  
Protonation Constant ◽  
Ion Pairing ◽  
Ion Pair ◽  
Enthalpy And Entropy Changes ◽  
Enthalpy And Entropy ◽  
Sodium Binding

The protonation constant (pKa) of SO42–(aq) has been determined at ionic strengths 0.5 M ≤I ≤4.0 M in NaCl and CsCl media at 25˚C by using Raman spectroscopy. These data were used to calculate the association constant of the NaSO4–(aq) ion pair in CsCl media. The results are in excellent agreement with previous values obtained by other techniques. The (pKa) was also measured at I = 4 M in both media at temperatures up to 85˚C and the associated enthalpy and entropy changes were calculated. However, reliable thermodynamic data for the ion-pairing reaction could not be obtained at higher temperatures probably because of competition from CsSO4–(aq).

Ion pair binding by an l-tyrosine-based polymerizable molecular receptor

2015 ◽  
Vol 39 (8) ◽  
pp. 6216-6222 ◽  
Author(s):  
Szymon Zdanowski ◽  
Jan Romański
Keyword(s):  
Ion Pairs ◽  
Functional Polymers ◽  
Ion Pair

A polymerizable molecular receptor able to bind ion pairs and new functional polymers containing the receptor units were synthesized and characterized.

Axle component separated ion-pair recognition by a neutral heteroditopic [2]rotaxane

2014 ◽  
Vol 50 (13) ◽  
pp. 1540-1542 ◽  
Author(s):  
Richard C. Knighton ◽  
Paul D. Beer
Keyword(s):  
Alkali Metal ◽  
Metal Cation ◽  
Alkali Metal Cation ◽  
Ion Pairs ◽  
Ion Pair ◽  
Sodium Cation ◽  
Halide Anion ◽  
Cooperative Recognition

A neutral heteroditopic pyridine N-oxide axle containing [2]rotaxane, synthesised via sodium cation templation, displays cooperative recognition of alkali metal cation-halide anion ion-pairs in an unprecedented axle component separated ion-pair binding fashion.

scholarly journals Conductometric studies of 1, 3, 5 –triazinothiocarbamide at different concentration and temperature

2021 ◽  
Vol 16 (2) ◽  
pp. 151-157
Author(s):  
DD Sonone ◽  
ME Shelke ◽  
DT Tayade
Keyword(s):  
Thermodynamic Parameters ◽  
Association Constant ◽  
Ion Association ◽  
Vital Role ◽  
Ion Pair ◽  
Pair Formation ◽  
Drug Diffusion ◽  
Ion Pair Formation

Conductivity plays vital role in drug diffusion. Thermodynamic parameters affected by substituents of drug. Thermodynamic parameters of 1, 3, 5 –triazinothiocarbamide (1a) have been investigated by using conductometrically carried out at different molar concentrations. This work highlights investigation of G, K and µ values. The thermodynamic parameters viz. ΔH, ΔS and ∆G for ion pair formation determine from the value of ion association constant. This technique is suitable and accurate to study of pharmokinetics and pharmodynamics parameters.

Isotope effects and activation parameters for the proton transfer reaction from 1-(4-nitrophenyl)-1-nitroethane to free anions and ion pairs of cesium n-propoxide in n-propanol solvent

1986 ◽  
Vol 64 (6) ◽  
pp. 1021-1025 ◽  
Author(s):  
Arnold Jarczewski ◽  
Grzegorz Schroeder ◽  
Przemyslaw Pruszynski ◽  
Kenneth T. Leffek
Keyword(s):  
Proton Transfer ◽  
Rate Constants ◽  
Isotope Effects ◽  
Ion Pairs ◽  
Activation Parameters ◽  
Solvation Shell ◽  
Ion Pair ◽  
Initial State ◽  
Free Ion ◽  
Deuteron Transfer

Rate constants for the proton and deuteron transfer from 1-(4-nitrophenyl)-1-nitroethane to cesium n-propoxide in n-propanol have been measured under pseudo-first-order conditions with an excess of base for four temperatures between 5 and 35 °C. Using literature values of the fraction of cesium n-propoxide ion pairs that are dissociated into free ions, separate second-order rate constants for the proton and deuteron transfer to the ion pair and to the free ion have been calculated. The cesium n-propoxide ion pair is about 2.8 times more reactive than the free n-propoxide ion. The primary kinetic isotope effects for the two reactions are the same (kH/kD = 6.1–6.3 at 25 °C) within experimental error. The enthalpy of activation is smaller for the ion-pair reaction and the entropy of activation more negative than for the free-ion reaction. For proton transfer, ΔH±ion pair = 8.3 ± 0.2 kcal mol−1, ΔH±ion = 9.6 ± 1.0 kcal mol−1, ΔS±ion pair = −12.3 ± 0.6 cal mol−1 deg−1, ΔS±ion = −10.1 ± 3.4 cal mol−1 deg−1. The greater reactivity of the ion pair relative to the free ion is interpreted in terms of the weaker solvation shell of the ion pair in the initial state.

Octahedral cobalt(III) complexes in dipolar aprotic solvents. II. Association between cis- and trans-dichlorobisethylenediamine cobalt(III) cations,[Co en2 Cl2]+, and chloride and bromide ions in the solvents NN-dimethylformamide, dimethyl sulphoxide, and LVN-dimethylacetamide

1966 ◽  
Vol 19 (1) ◽  
pp. 43 ◽  
Author(s):  
WA Millen ◽  
DW Watts
Keyword(s):  
Spectrophotometric Method ◽  
Ion Pairs ◽  
Ion Association ◽  
Ion Pair ◽  
Association Constants ◽  
Dimethyl Sulphoxide ◽  
Aprotic Solvents ◽  
Ion Association Constants ◽  
Cis And Trans ◽  
Dipolar Aprotic Solvents

Ion association constants at 30� have been determined for the cis-[Co en, Cl2]+Cl- ion pair in NN-dimethylformamide (DMF), NN-dimethylacetamide (DMA), and at 20.0�, 25.0�, and 30.0� in dimethyl sulphoxide (DMSO), by a spectrophotometric method. Association constants for the cis-[Co en2 Cl2]+Br- and the trans- [Co en2 Cl2]+Cl- ion pairs have also been determined in DMF at 30�.

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