Yes, we have donated miles.
Back when we used to have a 1k club here in Seattle, there would be times when the 1k club agents would call with very specific emergency cases where a people needed miles immediately to travel to a specialty hospital for treatment. In those circumstances we would donate miles.
I can remember one instance where a group of FlyerTalkers pitched in miles to fly a young girl and her parents to an east coast clinic for surgery, and then also donated a ticket for a nurse to fly back with the girl, post-surgery.
Donating under these types of circumstance is something I would happily do in the future. Just donating miles to an organization, without knowing how they will be used, makes me hesitate. Like Rudi, I would not feel good about flying charity administrative personnel around in first class.