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PC is a reactionary power so you use it when appropriate.
Outwit and Perplex are free actions that can be activate at any point during your turn ("at the beginning of your turn", during the middle of your turn, or "at the end of your turn) in which no other action is currently in mid resolution (you can't activate Charge and then try to Outwit before finishing doing Charge).
Using free actions can happen before or after the character took a non-free action. So yes, you can more and then use these abilities.
They groaned, they stirred, they all uprose, Nor spake, nor moved their eyes; It had been strange, even in a dream, To have seen those dead men rise.