In order for the drive to be BOOTABLE, it will have to be formatted as APM (Apple Partition Map).
APM does not support AFT (Advanced Format Technology) which is used on all drives over 2 TB xompletely. Misalignments between the logical and physical sectors will occure, and eventually, as the drive fills, data WILL be lost.
Drives over 2 TB will only work if the drive is formatted using GPT (GUID Partition Table), but if you format a drive with GUID on a G5 or any PPC Mac, it will NOT be bootable.
It should be possible to use one 2 TB drive formatted APM to boot from, and a 4 TB drive formatted as GUID to use as data storage only.
Bottom line: even if you get a 3 TB drive that is connected to a PCI card to boot by formatting it as APM you WILL eventually be very sorry you did so.