Hi Laura,
It's important to remember that insurance policies don't deal with divorces or separations. Insurance covers the vehicle and injuries resulting from the vehicle. The Buick is insured under John's policy, so this policy will pay for claims involving the vehicle.
There will be repercussions from this accident. I'm sure Mary's brother will ticketed and fined (maybe arrested) for driving without a license and John's insurance company may cancel his insurance for allowing an unlicensed driver to use the vehicle. But, John's insurance will pay the claim(s) because the Buick is a covered auto on the policy.
I hope this helps. Please let me know if you have other questions.
Jan