There are a couple effects that contribute to the problem, its not just one thing that does it.
First off, as said before, chips can be modeled as a capacitive load (well, for the most part anyway, its not a perfect model) and in a capacitive load the power dissipated in the load increases as the square of the voltage and linearly with frequency. So as you pump up the frequency and voltage, the heat that is dissapated by the heatsink will increase. This aggrivates the other problems that limit the chip but in and of itself isn't a limiting factor, since chips stop working well before they turn into molten blobs of silicon. If there were no other factors, then upping the voltage would just increase the heat output and make it stop working sooner, but we all know that voltage increases can make things more stable at higher clock speeds so this isn't the only factor.
If I'm remembering my class on chip design correctly, however, the main limit on chips is the rise time of the transistor. Hmm, I just realized I don't have my textbook handy, so I can't give an exact description. From memory: As you increase the frequency, the voltage needs to rise from a 0 to a 1 fast enough that it is stable before the next clock tick hits. We like to model transistors as simple 0s and 1s, but there is also a "who the heck knows" state in the middle where the output isn't certain to have switched states. So if the voltage doesn't rise fast enough to be definitely a 0 or a 1 before the next tick, you start getting errors in your calculations and it doesn't take long before this corrupts whatever was attempting to run on an unreliable circuit (which usually means your OS does something like find out that fase really equals true and commits suicide). Increasing the voltage makes the rise snd fall times faster, which means you can get past this problematical state quicker, which means the chip is more reliable at higher frequencies. However, rise time is not just a property of voltage it also involves the resistance of the wires and the silicon, so as the heat increases the resistance increases and the rise time starts slowing again.
So... increasing the clock frequency makes increased heat which increases the resistance of the silicon which slows the rise time which makes some of the signals not complete their 0 to 1 or 1 to 0 transitions in time. Raising the voltage quickens the rise time which might allow you to raise the clock frequency higher, but that just starts the cycle again. Giving it better cooling will lower the resistance of the silicon which quickens the rise time which makes the signals much more reliable and lets you clock it higher without increasing the voltage.
Thats all from memory of a class 3 years ago, but I think its at least in the ballpark.