I do not know if this odd issue is related or not. It was not with xfce4 but rather with Plasma. It occurred on 2 of the 3 upgrades I performed. I did not fully investigate, seems like maybe a timing issue, as to when ovs starts for NetworkManager. If I placed it in multi-user and disabled NetworkManager, rebooted and then and manually started NetworkManager, networking started fine. My SSD daily driver install was not effected.
It seems odd to have an After= in a systemd unit file without the service installed.
Edit: I went back and restored the NetworkManager-ovs.conf file on one of the SD installs and rebooted, twice just to make sure, and the issue no longer exists. If it occurs again, I will try to investigate further.