Solvent nucleophilicities of hexafluoroisopropanol/water mixtures
J. Phys. Org. Chem., 2013, 26 (1), 59-63 published on 26.11.2012
. First-order rate constants k1 for the trapping of various donor- and acceptor-substituted benzhydrylium ions in mixtures of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and water ranging from 50 to 99% HFIP (w/w) were determined by laser flash photolytic generation of benzhydrylium ions from benzhydryl triarylphosphonium salts in these solvents. From these rate constants, we derived the solvent-specific reactivity parameters N1 and sN for HFIP/water mixtures as defined by the linear free energy relationship lg k1(20 °C) = sN(N1 + E).