Infrared Spectrum of the Adamantane -Water Cation: Hydration-Induced C-H Bond Activation and Free Internal Water Rotation.

Diamondoid cations are reactive intermediates in their functionalization reactions in polar solution. Hydration is predicted to strongly activate their C-H bonds in initial proton abstraction reactions. To study the effects of microhydration on the properties of diamondoid cations, we characterize herein the prototypical monohydrated adamantane cation (C H -H O, Ad -W) in its ground electronic state by infrared photodissociation spectroscopy in the CH and OH stretch ranges and dispersion-corrected density functional theory (DFT) calculations. The water (W) ligand binds to the acidic CH group of Jahn-Teller distorted Ad via a strong CH⋅⋅⋅O ionic H-bond supported by charge-dipole forces. Although W further enhances the acidity of this CH group along with a proton shift toward the solvent, the proton remains with Ad in the monohydrate. We infer essentially free internal W rotation from rotational fine structure of the ν band of W, resulting from weak angular anisotropy of the Ad -W potential.