Sion Passive Bug with Tiamat
https://youtu.be/jjJXnMhDYQY?t=8m38s
So I tried it in practice tool, and if you die to an enemy champion, the passive splash damage does not work. If you kill a minion, then it begins to work. If you auto attack like an X amount of times, you might get it to work. Using the active would activate it again.
If you look at the video, the Sion got a few auto attacks off and none of them turned the splash damage on again.
I do not know if this affects other on-hit items, but I think this is a result of the Doom Bots. In the level 100 Gauntlet, Sion's passive damage does not work and I think that this bug has found it's way in to the P v P environment.