Where are you coming up with these wire sizes? In special cases, as in very long runs, you need different sizes. But if you are close to 100 ft give or take, the 2-2-4-6 aluminum should be good enough, and more easy to find since that is what everyone mostly uses.The only 2-2-4-6 MHF I can find is aluminum and I need 1 AWG for 100 amps.
The only wire I can find that O can go pick up is Southwire 1/0-1/0-1/0-2 aluminum wire for $551 + tax
If I want copper I'd have to order it online from a wire distributor.
3-3-3-5 is $885
2-2-2-4 is $1063
Huge difference in price from the aluminum.
The only reason you would need a #2 neutral, is if you had a 100 amp single pole breaker with something on the other end that would pull 100 amps or near it. That would be very very odd.
It's easy to think how this works. The power is A/C, so it goes one direction, turns around, and goes the other direction in the circuit 60 times a second. The two #2 wires will have 240v between them. But from each one of the #2's to neutral will be 120v. But these two "sides" , A phase and B phase of the 120v are out of phase. When one 120v circuit is pulling, the other 120v side is pushing.
If you have two 20 amp 120v circuit breakers, one on A phase to neutral, and the other on B phase to neutral, and both circuits perfectly draw 15 amps each, there will be zero amps on the neutral. One phase will be pushing 15 amps while at the same time the other phase will be pulling 15 amps. This cancels the current flow in the neutral.
If you have a circuit on A phase that draws 15amps, and another circuit on B phase that draws 10 amps, the current in the neutral will be 5 amps if these are the only two circuits in the panel.
This is why the neutral can be undersized. It will never see 100 amps in normal conditions.