Correlating solvent dynamics and chemical reaction rates using binary solvent mixtures and two-dimensional infrared spectroscopy.

Two-dimensional infrared (2D-IR) spectroscopy was performed on Vaska's complex (VC) and its oxygen adduct (V C-O2) in binary solvent mixtures of chloroform or benzyl alcohol in d6-benzene. The second order rate constants for oxygenation were also measured in these solvent mixtures. The rate constant in chloroform mixtures is linear with mole fraction within the error of the measurements but changes nonlinearly in benzyl alcohol mixtures, displaying a preference for the alcohol over benzene.