All other things being equal, I can see how relying on ECC *might* indeed allow you to operate a system a little bit further beyond spec than without, in the sense that the ECC might allow you to know when you start getting bad data, so that you could deal with it. But the gain might not be much (depends on the chips' internal details), and may not be something to rely on.
It's like overclocking your processor or video card: on a case by case basis, you can tweak, test, tweak, test, etc., until you get a decent boost and are still (mostly) crash-free... but it's hard to be certain and you might still get errors now and then, plus the result is only true for that specific chip.
On why ECC parts might have longer life... not sure. One guess would be that they're simply built/tested to higher standards because of the type of application / customer they envision for the devices with ECC vs. the basic ones, and the difference in the price people will pay...