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I can think of the "Evil Queen" and her Huntsman in versions of the "Snow White" story, or perhaps an "Evil Matriach" dotes on a favorite son, as in one of the "Shrek" stories, but I couldn't locate a specific trope for a villainess and her lone loyal male henchman.
Consider Evil vs. Evil if an villain turns against his boss, becoming a villain protagionist instead of an average antagionist.
Edited by PCD
I feel like there is a trope where a solo(not part of a team) antagonist(usually male) has a female master. Such as Angor Rot and Morgana in Trollhunters.