The file copying finished eventually. The tricky part was to switch to booting from the new Raid instead of the old, getting grub to read the correct kernel and pass the correct root. After a few rounds through booting from an USB image (#Ventoy ftw), and updating grub inside a chroot, it eventually worked.
Then I zeroed out the old RAID device, and ran mdadm with --grow and --raid-devices=2 to sync the new fs back to the old drive.
Took all day, and syncing those 2 terabytes takes a while longer still.
Let's hope this works out now...