First, make the buckeyes. In a medium bowl, stir together the peanut butter, vanilla, room temp butter, and powdered sugar (1/2 cup at a time). It will be very stiff once all the powdered sugar is added - keep mixing! The mixture should be stiff enough to roll into balls, but not too dry (it shouldn't crumble - if it does, add a bit more peanut butter or butter). Once mixed, scoop 1 tablespoon at a time and roll into 1-inch balls. Place on a waxed-paper-lined baking sheet or plate and once you've used all of the mixture and rolled it into balls, place them in the freezer to chill for 30 minutes. While balls are chilling, melt the chocolate in the microwave in 45 second intervals (stirring in between). Once balls are chilled, remove from freezer and use a fork to dunk each one into the chocolate mixture so they are completely covered. Let drip/dry back on the waxed paper baking sheet, then set aside while you make the cupcakes (there will be a few extras so you can eat one buckeye now!).
Next, make the cupcakes. Preheat the oven to 350° F and grease two 12-cupcake pans with either butter or cooking spray, or line with paper cupcake cups. In a medium bowl, sift together all of the dry cupcake ingredients (flour, sugar, cocoa powder, baking soda, baking powder, salt), and whisk to combine.
In a separate large bowl, whisk together the eggs, sour cream, canola oil, and vanilla extract until fully blended and creamy. Once combined, add in the dry ingredients and use a spatula or wooden spoon to mix. Fun step! Poor in that cup of piping hot coffee and stir until fully combined (it’ll take some working). Pour batter into the cupcake pans (each one should be about 2/3-3/4 full) and bake for 20-22 minutes or until a toothpick inserted into the middle of one of the cupcakes comes out clean. Remove from oven and let cool.
While the cupcakes are cooling, make the buttercream! First, peanut butter: In a large bowl, using an electric mixer, beat the room temp butter and peanut butter and vanilla until creamy. Add in the powdered sugar 1/2 cup at a time and beat on low until combined. Then add in the milk 1 tablespoon at a time - you want to get a consistency that's firm but not too stiff to pipe, it should be smooth and creamy looking. Spoon 1/2 of the frosting into a thick line onto a sheet of plastic wrap, and wrap it into a log, then set aside.
Then, the chocolate buttercream: In a medium bowl, using an electric mixer, beat the room temp butter and cocoa powder and vanilla until smooth. Add in the powdered sugar 1/2 cup at a time and beat on low until combined. Then add in the milk 1 tablespoon at a time - you want to get that same consistency that's firm but not too stiff to pipe, it should be smooth and creamy looking. Spoon 1/2 of the frosting into a thick line onto a sheet of plastic wrap, and wrap it into a log, then place both of the logs vertically into a piping bag with a piping tip inside (this will allow you to pipe the two flavors at once onto the cupcakes.
Before piping the buttercream onto the cupcakes, use a melon baller, paring knife, or large piping tip to cut a hole into the top of each of the cooled cupcakes as in the picture here. Fill each hole with one of the buckeyes.
Then pipe frosting onto the top of the cupcake+buckeye and serve!