Yeah, Prowl and Jazz would definitely fill the Zoe and Wash roles perfectly. The rest are more difficult; I would wind up playing mix-and-match with 'bots and 'cons both XD

...great, now I'm making a list.

Prowl - Zoe
Jazz - Wash
Ironhide - Mal (it just seems to work in my head XD)
Starscream - Jayne
Wheeljack - Kaylee
Shockwave - Simon (he can't shoot for shit)
Frenzy - River ("little crazy person")
Arcee - Inara
Skyfire - Book

And for the record, I cannot believe I just sat here for ten minutes trying to decide roles XD