2926-27-4Relevant articles and documents
In further pursuit of the carbene analogy: Preparation and crystal structure of (N,N,N′,N′-tetramethylethylenediamine)potassium [cis-ethene-1,2-di(tert-butylamido)]gallate(I)
Schmidt, Eva Susanne,Schier, Annette,Schmidbaur, Hubert
, p. 505 - 507 (2001)
The preparation and crystal structures of (N,N,N′,N′-tetramethylenediamine)potassium[cis-ethene-1,2-di (tert-butylamido)]gallate(I) were discussed. The structure of the compound consisted of dimeric structure with the potassium cations η5-coord
Lewis Acidity Scale of Diaryliodonium Ions toward Oxygen, Nitrogen, and Halogen Lewis Bases
Legault, Claude Y.,Mayer, Robert J.,Mayr, Herbert,Ofial, Armin R.
supporting information, (2020/03/13)
Equilibrium constants for the associations of 17 diaryliodonium salts Ar2I+X- with 11 different Lewis bases (halide ions, carboxylates, p-nitrophenolate, amines, and tris(p-anisyl)phosphine) have been investigated by titrations followed by photometric or conductometric methods as well as by isothermal titration calorimetry (ITC) in acetonitrile at 20 °C. The resulting set of equilibrium constants KI covers 6 orders of magnitude and can be expressed by the linear free-energy relationship lg KI = sI LAI + LBI, which characterizes iodonium ions by the Lewis acidity parameter LAI, as well as the iodonium-specific affinities of Lewis bases by the Lewis basicity parameter LBI and the susceptibility sI. Least squares minimization with the definition LAI = 0 for Ph2I+ and sI = 1.00 for the benzoate ion provides Lewis acidities LAI for 17 iodonium ions and Lewis basicities LBI and sI for 10 Lewis bases. The lack of a general correlation between the Lewis basicities LBI (with respect to Ar2I+) and LB (with respect to Ar2CH+) indicates that different factors control the thermodynamics of Lewis adduct formation for iodonium ions and carbenium ions. Analysis of temperature-dependent equilibrium measurements as well as ITC experiments reveal a large entropic contribution to the observed Gibbs reaction energies for the Lewis adduct formations from iodonium ions and Lewis bases originating from solvation effects. The kinetics of the benzoate transfer from the bis(4-dimethylamino)-substituted benzhydryl benzoate Ar2CH-OBz to the phenyl(perfluorophenyl)iodonium ion was found to follow a first-order rate law. The first-order rate constant kobs was not affected by the concentration of Ph(C6F5)I+ indicating that the benzoate release from Ar2CH-OBz proceeds via an unassisted SN1-type mechanism followed by interception of the released benzoate ions by Ph(C6F5)I+ ions.
Preparation method of trifluoromethane sulfonic acid
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Paragraph 0023; 0024; 0026; 0034, (2017/01/09)
The invention relates to a preparation method of trifluoromethane sulfonic acid. According to the preparation method, trifluoromethanesulphonyl fluoride and alkali metal hydroxide are subjected to a neutralizing hydrolysis reaction under existence of a fluorine fixing agent, after the reaction is completed, reaction liquid is filtered and dried, and fluorinated methyl sulfonic acid alkali metal salt is obtained; the fluorinated methyl sulfonic acid alkali metal salt and fuming sulphuric acid are subjected to acidizing treatment, then rectification is conducted multiple times, and high-purity trifluoromethane sulfonic acid is obtained. Through improvement of the preparation method, operating flexibility, production efficiency and product stability are improved, the comprehensive yield is raised, product purity can reach 99.90% or above, and the preparation method is suitable for industrial production.
