LAUSR

The importance of quantum-mechanical tunneling becomes increasingly recognized in chemical reactions involving hydrogen as well as heavier atoms. Here we report concerted heavy-atom tunneling in an oxygen-oxygen bond breaking reaction from cyclic beryllium peroxide to linear dioxide in cryogenic Ne matrix, as evidenced by subtle temperature-dependent reaction kinetics and unusually large kinetic isotope effects. Furthermore, we demonstrate that the tunneling rate can be tuned through noble gas atom coordination on the electrophilic beryllium center of Be(O2), as the half-life dramatically increased from 0.1 h for NeBe(O2) at 3 K to 12.8 h for ArBe(O2). Quantum chemistry and instanton theory calculations reveal that noble gas coordination notably stabilizes the reactants and transition states, increases the barrier heights and widths, and consequently reduces the reaction rate drastically. The calculated rates and in particular kinetic isotope effects are in good agreement with experiment.