If the junction-to-case thermal resistance is 0.5 deg C/W and CPU dissipates 100W, then the junction will operate at 50 deg C above the case temperature, whatever that is.
If the case is kept at room temperature (say 25 deg C), which is the best possible a simple air or water cooled system can do, then the junction will operate at 75 deg C.
For simple discrete transistors and diodes, Tj_max is typically 150-175 deg C. For modern CPUs I believe it's closer to 100-125 deg C.
Thus, lowering the case temperature means the chip can consume more power before reaching the maximum junction temperature.
A greater power budget means you could raise operating voltages to help with overclocking for example. Keep in mind power dissipation scales with voltage squared.
There might be other effects too, I'm no overclocking expert, but this is one aspect.
But not my field so no idea how that interplay works out.
Think of FET as a solid state thermionic valve, it's not that far away from it, if you dig into physics.