I didn't really think to bother with them too much either, I was over level 100 when I got em cause I'm finally getting to the point of grabbing all the perks I wanted now I can mess around.
they are sketchy about when they work as you have no idea if it IS going to work or not, and if your in sneak and fail they instantly find you, and it has kind of a short range.
so I started using them in a different priority. Sneak > Shootout > Pacify
If my cover is blown then I start trying, its fun when it works and there is actually a bunch of unique dialogue for all the individual creatures (the rad scorpion one was funny) my favorite so far is trying to grab deathclaws when I see them, or using it on raiders so I can line them up and execute them for there crimes 