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It's a more old Steve/tony fic, that have Steve going undercover in Natasha's place on Iron Man 2. And Tony only findining out who he is when Avengers happen.

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greengal82.livejournal.com

I think the fic you're looking for might be "one is desire (the other the means)" (https://archiveofourown.org/works/15674679/chapters/36415170) by newyorktopaloalto

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Steve goes undercover on Natasha's place