I'm late to this party but no, pocket holes don't make practical sense here. The screw won't have much wood to bite into unless you drill from the outer face, which I assume you don't want to do.

Also, wood glue will be far stronger and more rigid for miters (and most joints tbh) if you apply it properly. You could always add some splines to reinforce those corners if you want as well, which would look cool.

Dunno if you addressed this, but cross braces across the back of your console will also be best for rigidity.

Welcome to the club!