Probably Janeway in Scientific Method going for that pulsar trajectory on which Tuvok gave her <10% survival odds (IIRC). Even though there were extenuating factors.
I think I had her face a tribunal for that in some fanfiction or other (not only did she risk her own ship, but she caused the destruction of an alien vessel and the death of 30 or so crew). The judgment was that she was acquitted, due to extreme mental incapacity.
She also faced severe questions about Tuvix, but was not charged because there were no precedents for the rights of fused beings, or whether splitting them was actually murder.