Please reassure or correct me on 529 usage for student loan payments

I live in a state that allows me to deduct 529 contributions (up to $5800 per person) from my state income taxes, which are a bit over 8%.

My understanding is that I can use $10k in 529 funds to pay student loans. My wife still has plenty of those. SO:

If she and I each open a 529 with her as a beneficiary this year with $5000 in it, then immediately withdraw it, I should be able to deduct the full $10k from my taxes and just immediately close out the accounts.

I think?
I keep getting 3/4 through the way of the account setup and then second-guess myself.