If you're using [man]file_get_contents/man to store several megabytes of data in a variable, then I'd say sure, unset() the variable after you're done working with it if the script has more to do.
Likewise when working with image resources; [man]imagedestroy/man can free up the memory used so that you can create more image resources for the next image to be processed.
Other than situations like that, rowan is right - there's really no point in unset()'ing variables in a script. If you're that worried about RAM usage, it's time to upgrade your server 😉