When the brownies come out of the oven, make the icing. Place the powdered sugar in a large bowl. In a medium saucepan over medium heat, combine the butter, cocoa powder, and buttermilk. Bring just to a boil, stirring constantly. (It will separate and look oily. Don't worry, it will still mix in well with the powdered sugar.) Remove from the heat, pour into the powdered sugar, add the vanilla, and beat until smooth.
1/4 cup Unsalted butter, 3 tbsp Unsweetened cocoa, 3 tbsp Buttermilk, 2 1/4 cups Powdered sugar, 1/2 tsp Vanilla extract