My first was in a 5-morning program starting a couple weeks before she turned 3. My second just started a 3-day program, at 2.5.
Both did/are doing great, but as a SAHM, my preference is the 3-day program (obviously if you need the child care it's different, and still fine for the kid). With the two days off, we have time for one-on-one playdates, which I think is important for developing friendships. We have time for a morning gymnastics class, so I can still participate in structured things like that. We have time to just be together, which, since that's one of the reasons I chose to SAH, is important to me.
But I don't think any of that particularly matters to the kid. If you have other reasons to want 5-day -- you have a younger child at home, you need the child care, you like the school better -- that can easily be more important than any of the 3-day advantages.