Pygon
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I'm going to look this up to confirm, but I believe they get extra spells when they have brains in their sacs, and they lose one spell when they absorb a brain for special uses.
After reading: I see 4 extra 1st, 2nd and 3rd level spells. The end of the stat block assumes the Collector has a full complement of 12 brains. That's for the Collector stats in the appendix. Looking at the loremaster one now...
I see 12 extra spells on the loremaster Collector as well. He must have 12 brains, too.