Synthesis and physical properties of tris(dialkylamino)cyclopropenium bistriflamide ionic liquids

Walst, Kelvin J.; Yunis, Ruhamah; Bayley, Paul M.; MacFarlane, Douglas R.; Ward, Callum J; Wang, Ruomeng; Curnow, Owen J.

doi:10.1039/c5ra05254h

Cited by 24 publications

(45 citation statements)

References 76 publications

(32 reference statements)

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“…DT1 was successfully synthesized and characterized by 1 H NMR, 13 C NMR, and high resolution mass spectrometry (HRMS) and its purity was confirmed by liquid chromatography‐mass spectrometry (LCMS). However, DMSO and chloroform solutions of DT1 decompose within few hours to give complex mixtures of ring‐opened products (Figure S1) …”

Section: Resultsmentioning

confidence: 99%

Deltamides and Croconamides: Expanding the Range of Dual H‐bond Donors for Selective Anion Recognition

Zwicker

Yuen

Smith

et al. 2017

Chemistry A European J

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Dual H-bond donors are widely used as recognition motifs in anion receptors. We report the synthesis of a library of dual H-bond receptors, incorporating the deltic and croconic acid derivatives, termed deltamides and croconamides, respectively, and a comparison of their anion binding affinities (for monovalent species) and Brønsted acidities to those of the well-established urea and squaramide dual H-bond donor motifs. For dual H-bonding cores with identical substituents, the trend in Brønsted acidity is croconamides>squaramides>deltamides>ureas, with the croconamides found to be 10-15 pK units more acidic than the corresponding ureas. In contrast to the trends displayed by ureas, deltamides and squaramides, N,N'-dialkyl croconamides displayed higher binding affinity to chloride than the N,N'-diaryl derivatives, which was attributed to partial deprotonation of the N,N'-diaryl derivatives at neutral pH. A number of differences in anion binding selectivity were observed upon comparison of the dual H-bond cores. Whereas the squaramides display similar affinity for both chloride and acetate ions, the ureas have significantly higher affinity for acetate than chloride ions and the deltamides display higher affinity for dihydrogenphosphate ions than other oxoanions or halides. These inherent differences in binding affinity could be exploited in the design of anion receptors with improved ability to discriminate between monovalent anions.

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Section: Resultsmentioning

confidence: 99%

Deltamides and Croconamides: Expanding the Range of Dual H‐bond Donors for Selective Anion Recognition

Zwicker

Yuen

Smith

et al. 2017

Chemistry A European J

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“…[28] Hysteresis and passivation were observed for cases 1 and 2 at the GC electrode, consistent with the electrochemistry of the cation rather than the [Tf 2 N] À anion;o xidation was also more facile at the platinum electrode. Although multiple authors have reported anionsl imitingt he reductive electrochemical window of ionicl iquids, [32] the resultsd escribed here are only the second example after that of the cyclopropenium salts reported by Curnow et al [33] of an ionic liquid cation limiting the oxidative window of an ionic liquid.…”

Section: Electrochemical Windows Of Ionic Liquids1-3 and 10mentioning

confidence: 57%

Novel Chloroimidazolium‐Based Ionic Liquids: Synthesis, Characterisation and Behaviour as Solvents to Control Reaction Outcome

et al. 2016

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Novel ionic liquids containing chlorine atoms on the imidazolium cation were synthesised. The physicochemical properties of these ionic liquids were investigated extensively, including glass transition, melting and decomposition temperatures, density, viscosity, miscibility with common solvents and electrochemical window. The behaviour of these ionic liquids as solvents was examined through temperature‐dependent kinetic analyses on two reactions: a nucleophilic aromatic substitution (SNAr) reaction and a bimolecular nucleophilic substitution (SN2) reaction. The properties and effects on reaction outcome of these new ionic liquids were shown to correlate with the change in the nature of the cation.

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“…CH 2 Cl 2 , CHCl 3 , diethylether, ethanol, petroleum ether, D 2 O, tributylamine, dibutylamine and bis(2,2,2‐trifluoroethyl)amine were obtained commercially. [C 3 (NMe 2 ) 3 ]Cl was prepared by a literature method . Solvents were dried using an in‐house solvent purification system.…”

Section: Methodsmentioning

confidence: 99%

A Series of Discrete Dichloride Dihydrates: Characterisation and Symmetry Effects

et al. 2020

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A series of three discrete dichloride dihydrates [Cl2(H2O)2]2− have been isolated with different triaminocyclopropenium (TAC) cations and with different crystallographic symmetries. The cluster exhibits D2h symmetry with the tris(dimethylamino)cyclopropenium cation [C3(NMe2)3]+, C2h symmetry with the fluorinated cation [C3(N(CH2CF3)2)(NBu2)2]+ (containing two 2,2,2‐trifluoroethyl substituents) and C2v symmetry with the more fluorinated [C3(N(CH2CF3)2)2(NBu2)]+ cation. The effect of symmetry on the infrared spectra of the dichloride ion‐pair clusters, as well as deuterated analogues, has been investigated. The D2h‐ and C2h‐symmetric clusters each exhibit two stretching bands in the infrared at 3427 and 3368 cm−1 for D2h symmetry and 3444 and 3392 cm−1 for C2h symmetry, whereas the C2v‐symmetric cluster exhibits three bands at 3475, 3426 and 3373 cm−1. Computational studies were carried out on a [Cl2(H2O)2]2− cluster with C2v symmetry to aid the infrared band assignments.

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Synthesis and physical properties of tris(dialkylamino)cyclopropenium bistriflamide ionic liquids

Abstract: An investigation of symmetry (D3h, C3h, C2v and Cs) and alkyl chain length (6–60 alkyl carbon atoms) effects on the physical properties of peralkylated triaminocyclopropenium bistriflamide salts.

Cited by 24 publications

References 76 publications

Deltamides and Croconamides: Expanding the Range of Dual H‐bond Donors for Selective Anion Recognition

Deltamides and Croconamides: Expanding the Range of Dual H‐bond Donors for Selective Anion Recognition

Novel Chloroimidazolium‐Based Ionic Liquids: Synthesis, Characterisation and Behaviour as Solvents to Control Reaction Outcome

A Series of Discrete Dichloride Dihydrates: Characterisation and Symmetry Effects

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