Don't do that. :-)
[lwall] In Perl 4, you were not allowed to modify a hash at all while iterating over it. In Perl 5 you can delete from it, but you still can't add to it, because that might cause a doubling of the hash table, in which half the entries get copied up to the new top half of the table, at which point you've totally bamboozled the iterator code. Even if the table doesn't double, there's no telling whether your new entry will be inserted before or after the current iterator position.
Either treasure up your changes and make them after the iterator finishes or use keys to fetch all the old keys at once, and iterate over the list of keys.