Recently, we have formulated a concept going beyond the traditional relationship between thermodynamics and kinetics, which includes the effect of off-diagonal thermodynamics on reactivity. Here, I will present the latest advances in the concept. Among others, this will cover the discussion of the difference between H-atom transfer and proton-coupled electron transfer in terms of the relationship between thermodynamics and reactivity, and in relation to the predictability of reaction selectivity from thermodynamics. Also, I will show how the off-diagonal thermodynamics controls the shift from proton-coupled to hydride-coupled electron transfer. If time allows, I will also touch on some additional aspects of the concept, such as the connection of the off-diagonal thermodynamics with some electronic-structure descriptors.