37181-39-8Relevant articles and documents
Group Transfers III. Consequences of the Application of the Marcus Equation
Lewis, Edward S.
, p. 259 - 262 (2007/10/02)
The rates of many group transfers are well described by the Marcus equation.Alkyl transfers in the solvent sulfolane, the formal transfers of R+ from one nucleophile to another, fit almost within experimental error.In these fairly slow reactions the Marcus quadratic term is negligible.Neglect of this term leads to absence of Reactivity Selectivity principle correlations.It leads to a scale of nucleophilicities and one of methylating power.In contrast, many nonalkyl transfers have much lower intrinsic barriers, and neglect of the quadratic term is unjustifiable.For alkyl transfers there is no general correlation between rate and equilibrium constants.When closely related series, such as a Hammett variation in the leaving group or nucleophile are studied, there is generally a rate-equilibrium LFER.From the slope of this rate-equilibrium LFER, the charge, δ, on the transferring group is calculated.The variation in this charge, which is structurally plausible, gives a new perspective on the rates of SN2 reactions, including benzylic, and α-halocarbonyl systems.
Studies on trifluoromethanesulfonic acid. Part 2. Conductivities of solutions of metal trifluoromethanesulfonates and other bases in trifluoromethanesulfonic acid
Russell, David G.,Senior, John B.
, p. 22 - 29 (2007/10/02)
Electrical conductivity measurements are reported for solutions in trifluoromethanesulfonic acid of a number of simple and complex bases, including univalent and divalent metal trifluoromethanesulfonates.The univalent metal salts, water, aniline, and acetic acid behave as fully dissociated bases, while the alkaline earth metal salts show considerable ion association.The trifluoromethanesulfonate anion appears to have an abnormally high mobility, as compared to the metal cations, and is believed to conduct by a proton-transfer mechanism.Dissociation constants for some weak organic bases and association constants for strontium and barium trifluoromethanesulfonates are estimated.Sulfuric acid behaves as a weak electrolyte, while sulfur trioxide is effectively a non-electrolyte.The conductivities of potassium nitrate and potassium dihydrogenphosphate are consistent with the formation of the nitryl cation and the phocphate acidium ion, respectively.
