18716-27-3Relevant academic research and scientific papers
The versatile chemistry of niobium pentachloride with aliphatic amines: Aminolysis, metal reduction and C-H activation
Bondi, Riccardo,Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
, p. 192 - 198 (2015)
The reactions of NbCl5 with limited amounts (1-2 molar equivalents) of a series of primary, secondary and tertiary amines were investigated in dichloromethane as solvent. The 1:1 reaction of NbCl5 with NHEt2 cleanly afford
Proton transfers among oxygen and nitrogen acids and bases in DMSO solution
Ritchie, Calvin D.,Lu, Shanzheng
, p. 7748 - 7756 (2007/10/02)
Rate constants for the proton-transfer reactions between conjugate acids and bases of several amines, phenols, carboxylic acids, and the solvated proton in DMSO-d6 at 20 °C have been determined by the use of NMR line-shape analysis. Equilibrium constants for the same reactions are obtained from the pKa's of the acids in dimethyl sulfoxide, some of which have been reported in earlier work and the rest obtained in the present work by use of Bordwell's indicator techniques. All of the reactions have rale constants considerably below expected diffusion-controlled limits for the proton transfers in the thermodynamically favorable direction, and several of the reactions, including the identity reactions of carboxylic acids, have kinetic deuterium isotope effects, kH/kD, between 0.8 and 1.3. For reactions of N,N-dimethylbenzylammonium ion with several phenoxides, carboxylates, and solvent, the rate constants for transfers in the unfavorable directions show a reasonable Bronsted correlation with β ≈ 1 and a reasonably constant reverse rate constant of ≈3 × 106 M-1 s-1. The data clearly indicate that the proton-transfer step is not rate-limiting in these reactions. Most likely, desolvation is involved in the rate-limiting steps, but the rate constants are not simple functions of acidities as might have been expected if hydrogen bonding of acid to solvent were the major factor involved in the solvation Other factors, particularly dispersion interactions of solvent with solutes, are discussed. We suggest that the formation of an acid-base complex with proper orientation to allow contact between the proton and the basic site is rate-determining and involves desolvation along with detailed steric interactions of the acid-base pair.
