I think the term "Mechromancer" was popularized by the playable character Gaige from Borderlands 2. So it's probably a combination of being cute and of drawing on a verbal similarity to the necromancer (as bradknowles says).
I mean, if you want to get really technical, the "-mancy" suffix originally just referred to divination. So you have necromancy for divining the future by casting bones, or gyromancy for divining through spinning around, or geomancy for divining with rocks and dirt. The meaning later shifted to a more general "doing mystical stuff with" definition.
Probably it would be more thematic to come up with a more science-y term, but "Droid Boss" doesn't have quite the same ring to it.