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Dude as hot as she is I wouldn't take it. Even if I liked her and she liked me it would be very very hard to start a relationship or do the whole friends with benefits thing. My only reason being is that I value my friends a lot. If your bro is great to you and a super person overall, then don't lay hands on his ex. However if he's a total douche and you don't think you're going to be friends your whole life, then MAYBE.
But even if you are adamant on going for her, wait at least a bit so it doesn't look suspicious and get permission from his side. Rumours spread and it's never pretty. Try closing all ties before even going in.
Here's the thing that would stop me the most. If you want your bro's aftertaste, why don't you just get it from the source. It's a little bit disgusting to me when your bro has done that in there. I mean if it's a stranger you'll never know. But she's gonna be comparing you to your bro because you guys are so close. And stuff like that is bound to happen.
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