Re: Pepper Potts as Rescue
Yes they have at one time or another. Pepper is different in that she is in danger far more often than those you mention.
Tony is also in love with her. I'm sure he cares about those other people around him but he is not in love with them. People do crazy things to protect the people they love, I'm sure Tony is no exception.
If you are a supervillain, what's the best way to hurt a superhero who's identity is public to the world? IMO it would be going after the people they love.