ByeEnzo,
Engine management and programming is one of my favorite topics and we could (and happily!) go on and on about it. I'll give the 30-second summary. All OBDII cars (1996+) have an ECU that runs in closed-loop or open-loop mode. (There are other modes like warm-up, etc, but we'll ignore for now.)
In "normal" driving a car is in closed-loop, applying fuel injector pulse durations and then checking the O2 sensors to achieve an ideal 14.7:1 A/F ratio (stoichiometric). It does this many times per second and IT WILL rapidly achieve stoich. BTW, if the ECU cannot achieve stoich it will very rapidly issue a Check Engine Light.
BUT.... modern fuel injected cars ar not designed to run at stoich ALL of the time. Under load (quick acceleration, steep hills, etc.) engines need to run richer (more fuel) to prevent detonation. The problem is that O2 sensors (despite common belief) can only tell the computer if the A/F is above or below stoich. In the closed-loop scenario above, the ECU is fiddling around "walking the fence" of above/below/above/below stoich. As the O2's ARE COMPLETELY USELESS for anything other than reporting on stoich, manufacturers must have other means. This is open-loop mode. So, as you depress that gas pedal, at some point the ECU will seamlessly jump out of closed-loop in favor of open loop (running richer). It achieves the "running richer" by looking at the quantity of air being ingested through the mass air and using internal, factory-programmed values to hit these richer values. The trouble is that it has no feedback loop (hence the name of "open loop"), to know if it achieved the value or not. It could easily run either rich or lean and not know it.
Finally, to your question of the smaller (more boost) pulley. You'll be fine in closed-loop (light to mid throttle applications.) However, you will go into the danger zone when your car jumps to open-loop. The internal algos are now out of whack, and despite the car "sees" the amount of incoming air, the slopes of the computations have changed and your engine COULD be running lean. A lean supercharged motor = "Boom!"
In summary, 16psi pulley and drive like Grandma = OK.
16psi pulley and drive GT as you should = potential disaster.
Get a tune.