I think the more you ask probing questions the more you come across as interfering, and the less you leave her with her dignity.
If you send her a message and say, can we meet for coffee, there's something I want to discuss with you. Then start by saying: you don't know much about your relationship, they may not be exclusive, and this may all be rubbish but someone said something and you want to make sure she has the information. Tell her what your friend said, and say; look friend, you know enough to know if this is plausible, or overlapped dates, or is an issue, I just wanted to let you know you don't have to discuss it further with me.
If she wants to give him another go, she can then say to you, oh that ex is stirring, or we were not seeing other people till then, or even just I don't believe it. She can go away and think about it.
If t y ask probing questions and get her to say 'oh it's going great, we're exclusive since the start, in head over heels' then she'll feel humiliated and like you were setting her up if you then reveal he's a twat.
I think you should tell her, but no probing questions first.