5.2 is a buffer, as far as I am aware, which means that it will lock in the pH at 5.2 regardless of where the mash pH naturally sits for any particular grist/water combination. This means it'll bring up the pH if it's too low and lower if it it's too high. This negates the need for correct calcium in the mash to achieve the correct pH, but calcium additions should still be made for the other steps, as well as providing some thermal protection for amylases during the mash.
I am not certain how the buffering action of 5.2 alters calcium levels in the mash because I don't know the exact mechanism of action, but considering that most water is deficient in calcium it is always a good idea to add some mineral salts to boost the calcium concentration.