The Deadly Assassin is also a prime candidate for release, being that it's a great and noisy classic. So make that the second disk of the set - obviously, this is also a key Master episode and an interesting one for his character.
Plus, like with Beneath the Surface box, they seem keen to package a non classic in with classics to make them sell. In this case, The King's Demons is my vote for a third disk. At only two parts, and supposedly trite ones at that, it'd be hard to sell it any other way. It balances the Masters, and gives you three different Doctors in one box. I've always considered their conversation over Kamelion to be one of the most telling in their relationship, anyway, and thus important for a boxed set about the Master's character.
Add a few nice special features. Serve with red wine. Sorted. Christmas, please?
I've heard rumours that a Planet of Fire commentary has been recorded. I'm also sure that one day, someone who isn't me will realise the commercial brilliance of releasing a Black Guardian boxed set...