Preheat the oven to 350°F. Grease the bottom and sides of three 8-inch cake pans with nonstick cooking spray or baking spray. Line them with parchment paper rounds. Lightly grease the surface of the parchment paper and dust with cocoa powder.
Melt Chocolate: In a medium-sized heatproof bowl, combine 6 ounces of chocolate chips with the hot coffee and 1 tablespoon vanilla extract. Let the mixture sit for five minutes and then stir until smooth. Set aside.
Cake Batter: In a large bowl, use a whisk to sift together the flour, ¾cup cocoa powder, baking powder, baking soda and salt. Set aside.
Combine the sugar, eggs, and vegetable oil in a separate large bowl beating with a handheld mixer on medium speed until light and fluffy.
Add the sour cream and melted chocolate. Continue to beat on medium speed until fully combined.
By hand, use a large nonstick rubber spatula to fold the dry ingredients into the wet ingredients in two batches, mixing until just combined after each addition. Do not over-mix the batter!
Divide the batter evenly between the prepared pans. Transfer the batter to the prepared cake pans. Place the cake pans in the oven and bake for 18-20 minutes or until a toothpick comes out clean when inserted into the center of the cake. Set aside to cool for 5 minutes. Remove the cakes from their pans, place them on a wire rack, and cool completely or refrigerate for 30 minutes.
Make the Frosting: In a large bowl, beat 1 ¼ cups butter with a hand mixer until light and fluffy; add the peanut butter and remaining one tablespoon vanilla extract and continue beating until smooth. With the mixer on low speed, add the powdered sugar 1 cup at a time and the water, mixing just until combined. Set aside.
Place a dollop of frosting in the center of your cake plate or cake stand. Position the first cake layer on top. Spoon 1 ¼ cups of frosting on the cake layer and smooth it out using an offset spatula. Repeat with the second and third layers. Frost the top and sides of the cake. Chill to set.
Make the Ganache: In a medium saucepan, combine the heavy whipping cream, one tablespoon butter, and light corn syrup. Heat on low until the butter has melted and the cream is hot (but not boiling). Remove the hot cream from the heat. Add the remaining 6 ounces of chocolate chips. Let the mixture stand for 3 to 5 minutes until the chocolate has melted, then stir until completely smooth.
Allow the ganache to cool to room temperature, but it should still be pourable. Place the assembled cake on a wire rack on top of a baking sheet and pour the ganache over the top and sides of the cake. Re-use any ganache that has dripped onto the baking sheet. Smooth the ganache-covered cake with an offset spatula. (You can gently reheat the ganache as needed in a saucepan or in the microwave.)
Refrigerate the cake for 2 hours to allow the ganache to set. Pipe the top of the cake with the remaining frosting and decorate with Reese’s Miniature Peanut Butter Cups. Transfer to a cake stand or large serving plate and serve.
Store leftovers in an airtight container chilled in the refrigerator for up to 5 days.
Special Note: To make the cake easier to move around, assemble the cake on an 8-inch cake board. These are inexpensive and can easily be found where baking supplies are sold. This will allow you to move the cake from the wire rack after drizzling with the ganache to the fridge and ultimately to a cake stand for serving without touching the cake.