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Date: 2012-10-22 04:47 pm (UTC)Hypotenuse (http://archiveofourown.org/works/227890) by derryderrydown
Steve breaks up with Tony because he's in love with Iron Man. That's when things start to get complicated.
Keep Your Enemies Closer (http://archiveofourown.org/works/487351/chapters/849664) by kepteinen
Tony, fed up with the corruption in the superhero business, becomes a supervillain. SHIELD calls in Steve Rogers to fight him, which would be fine - if they didn't also ask Tony Stark to help as an engineering specialist.
I would particularly love it if you shared any others you happen to find that are off AO3, or untagged and relatively 'unfound gems," as I'm just as much a fan of this trope.
Edit: Oh hey look. I found more. Apologies in advance if I'm spamming you with fic/lists you've already stumbled across. Also, additional apologies for giving you a lot of fic that I haven't yet read and therefore cannot personally recommend. I have plans to go through this myself at some point.
Fic:
skund's It's the Sky that Makes the Ocean Blue (http://archiveofourown.org/works/111138).
Written for [livejournal.com profile] fictionalknight for her (belated) birthday prompt of Steve/Tony, explosion, with a bonus prompt of defenestration (the act of throwing something out a window). An emergency at the Avengers Tower leads to a revelation, and happy endings are only in story books.
Games (http://avengerkink.livejournal.com/7940.html?thread=15394308)
Duels always end in the victor marrying the damsel in distress. One day, Tony Stark is kidnapped and Captain America duels Iron Man for the fair Tony's hand. Captain America is very pleased by how impressed Tony Stark is over his great feat. Tony Stark is also very pleased with himself.
Fic Lists:
http://kink-finders.dreamwidth.org/30752.html?thread=366880 (All Steve/Tony, includes non-A03 hosted fics.)
http://melannen.dreamwidth.org/299787.html (Just a huge heap of identity porn fics, from various fandoms. Haven't looked through it all yet, but there might be a couple of Avengers fics in there. Or other fandoms that may interest you.)