Ferrocene-Containing Sterically Hindered Phosphonium Salts

The synthesis and physical properties of the series of the ferrocenyl-containing sterically hindered phosphonium salts based on di(tert-butyl)ferrocenylphosphine is reported. Analysis of voltamogramms of the obtained compounds revealed some correlations between their structures and electrochemical properties. The elongation of the alkyl chain at the P atom as well as replacement of the Br− anion by [BF4]− shifts the ferrocene/ferrocenium transition of the resulting salts into the positive region. DFT results shows that in the former case, the Br− anion destabilizes the corresponding ion pair, making its oxidation easier due to increased highest occupied molecular orbital (HOMO) energy. Increased HOMO energy for ion pairs with the Br− ion compared to BF4− are caused by contribution of bromide atomic orbitals to the HOMO. The observed correlations can be used for fine-tuning the properties of the salts making them attractive for applications in multicomponent batteries and capacitors.

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

10.26434/chemrxiv.7057892.v1 ◽

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.

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

Molecules ◽

10.3390/molecules26092751 ◽

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.

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

New Journal of Chemistry ◽

10.1039/c5nj01063b ◽

2015 ◽

Vol 39 (8) ◽

pp. 6216-6222 ◽

Cited By ~ 13

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.

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

Chemical Communications ◽

10.1039/c3cc48905a ◽

2014 ◽

Vol 50 (13) ◽

pp. 1540-1542 ◽

Cited By ~ 24

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.

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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

Canadian Journal of Chemistry ◽

10.1139/v86-171 ◽

1986 ◽

Vol 64 (6) ◽

pp. 1021-1025 ◽

Cited By ~ 4

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.

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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

Australian Journal of Chemistry ◽

10.1071/ch9660043 ◽

1966 ◽

Vol 19 (1) ◽

pp. 43 ◽

Cited By ~ 15

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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