Two state reactivity (TSR) and hydrogen tunneling reaction kinetics measured in the Co mediated decomposition of CHCHO.

The electronic structure of a transition metal atom allows it to act as a catalytic active site by providing lower energy alternative pathways in chemical transformations. We have identified and kinetically characterized three such pathways in the title reaction. One is an adiabatic pathway that occurs on a single potential energy surface described within the Born-Oppenheimer approximation.

Measurement of time dependent product branching ratios indicates two-state reactivity in metal mediated chemical reactions.

For several decades, the influence of Two State Reactivity (TSR) has been implicated in a host of reactions, but has lacked a stand-alone, definitive experimental kinetic signature identifying its occurrence. Here, we demonstrate that the measurement of a temporally dependent product branching ratio is indicative of spin inversion and is a kinetic signature of TSR. This is caused by products exiting different hypersurfaces with different rates and relative exothermicities.