Ultrafast two-dimensional infrared spectroscopy and molecular dynamics simulations of Mn(2)(CO)(10) in a series of linear alcohols reveal that the rate of intramolecular vibrational redistribution among the terminal carbonyl stretches is dictated by the average number of hydrogen bonds formed between the solute and solvent. The presence of hydrogen bonds was found to hinder vibrational redistribution between eigenstates, while leaving the overall T(1) relaxation rate unchanged.