Modelling catalytic turnover frequencies in ionic liquids: the determination of the bimolecular rate constant for solvent displacement from [(C6H6)Cr(CO)2Solv] in 1-n-butyl-3-methylimidazolium hexafluorophosphateElectronic supplementary information (ESI) available: synthesis of RTILs. See http://www.rsc.org/suppdata/cc/b3/b315781d/

Swiderski, Konrad; McLean, Andrew J.; Gordon, Christopher P.; Vaughan, D. H.

doi:10.1039/b315781d

Cited by 14 publications

(1 citation statement)

References 7 publications

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“…Most deviations from the behavior laid out in the Hughes−Ingold rules can be attributed to specific interactions, such as hydrogen bonding, which are not taken into account. Applications of the Hughes−Ingold approach to ionic liquids for a variety of reaction classes have had some limited success. ,− …”

Section: Introductionmentioning

confidence: 99%

Nucleophilic Reactions at Cationic Centers in Ionic Liquids and Molecular Solvents

Ranieri

Hallett

Welton

2007

Ind. Eng. Chem. Res.

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We report a quantitative comparison of the rates of nucleophilic reactions in ionic liquids and molecular solvents taking place at a cationic center. Cationic sulfonium electrophiles were reacted with three amine nucleophiles (n-butylamine, di-n-butylamine, and tri-n-butylamine) in several molecular solvents (toluene, dichloromethane, tetrahydrofuran, acetonitrile, and methanol) and ionic liquids {1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and 1-butyl-3-methylimidazolium trifluoromethanesulfonate}. The solvent effects on these reactions are examined using a linear solvation energy relationship based on the Kamlet−Taft solvent scales (α, β, and π*). These correlations reveal that hydrogen-bonding interactions provide the dominant effects in determining the rate of reaction. In particular, hydrogen bonds donated by the sulfonium electrophile to the solvent are the most important controlling factor on the rate of nucleophilic reaction.

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Section: Introductionmentioning

confidence: 99%

Nucleophilic Reactions at Cationic Centers in Ionic Liquids and Molecular Solvents

Ranieri

Hallett

Welton

2007

Ind. Eng. Chem. Res.

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Transition‐State Effects of Ionic Liquids in Substitution Reactions of Pt^II Complexes

Weber¹,

Puchta²,

Hommes³

et al. 2005

Angewandte Chemie

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Wenn Normalsein überrascht: Bei der Untersuchung eines Ligandenaustauschs an einem PtII‐Komplex (siehe Bild; apa: 2,6‐Bis(aminomethyl)pyridin) in Wasser, Methanol und der ionischen Flüssigkeit 1‐Butyl‐3‐methylimidazolium‐bis(trifluormethylsulfonyl)amid stellte sich heraus, dass sich die ionische Flüssigkeit „normal“ verhält, d. h. wie jedes andere Solvens. Änderungen in der Polarität des Übergangszustands spielen in ihr nur eine untergeordnete Rolle.

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Transition‐State Effects of Ionic Liquids in Substitution Reactions of Pt^II Complexes

et al. 2005

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When normal is a surprise: Studies of a ligand‐substitution reaction of a PtII complex (see picture; apa: 2,6‐bis(aminomethyl)pyridine) in water, methanol, and the ionic liquid 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)amide reveal that the ionic liquid behaves “normally”, that is, as any other solvent. In the ionic liquid, changes in the polarity of the transition state only play a minor role.

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Abstract: The bimolecular rate constant for solvent displacement, k(2), from [(C(6)H(6))Cr(CO)(2)Solv] by an incoming ligand has been determined in the room temperature ionic liquid, [bmim][PF(6)], and is compared to that for the same process in cyclohexane and dichloroethane.

Cited by 14 publications

References 7 publications

Nucleophilic Reactions at Cationic Centers in Ionic Liquids and Molecular Solvents

Nucleophilic Reactions at Cationic Centers in Ionic Liquids and Molecular Solvents

Transition‐State Effects of Ionic Liquids in Substitution Reactions of Pt^II Complexes

Transition‐State Effects of Ionic Liquids in Substitution Reactions of Pt^II Complexes

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Abstract: The bimolecular rate constant for solvent displacement, k(2), from [(C(6)H(6))Cr(CO)(2)Solv] by an incoming ligand has been determined in the room temperature ionic liquid, [bmim][PF(6)], and is compared to that for the same process in cyclohexane and dichloroethane.

Cited by 14 publications

References 7 publications

Nucleophilic Reactions at Cationic Centers in Ionic Liquids and Molecular Solvents

Nucleophilic Reactions at Cationic Centers in Ionic Liquids and Molecular Solvents

Transition‐State Effects of Ionic Liquids in Substitution Reactions of PtII Complexes

Transition‐State Effects of Ionic Liquids in Substitution Reactions of PtII Complexes

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Product

Resources

About

Transition‐State Effects of Ionic Liquids in Substitution Reactions of Pt^II Complexes

Transition‐State Effects of Ionic Liquids in Substitution Reactions of Pt^II Complexes