Preheat the oven to 350°F (175°C). Line a 12-cup cupcake pan with liners and lightly spray them with non-stick spray.
In a microwave-safe bowl (or small saucepan), combine 2.5 tablespoons oil, 1 stick melted butter (for batter), and 1/2 cup semi-sweet chocolate chips. Melt in 30-second intervals, stirring between each, until smooth; whisk and set aside to cool slightly.
In a medium bowl sift or whisk together 3/4 cup + 2 tablespoons all-purpose flour, 1/2 teaspoon baking soda, 1 teaspoon baking powder, 1/2 cup sifted unsweetened cocoa powder, and 1/2 teaspoon salt; set aside.
In a large bowl whisk 2 large eggs, 1 large egg yolk, 1 cup granulated sugar, and 1 teaspoon vanilla until smooth. Whisk in the cooled chocolate/butter/oil mixture until combined.
Add half of the dry ingredients to the wet mixture, then half of 1/2 cup buttermilk; gently fold until just combined. Repeat with the remaining dry ingredients and buttermilk. Do not overmix.
Quickly stir in 1/2 cup hot water until evenly combined; the batter will be thin. Fill each lined cup about 3/4 full. You may have batter for more than one pan.
Bake for 16–18 minutes, or until a toothpick inserted in the center comes out clean. Repeat with remaining batter if needed. Cool cupcakes completely on a wire rack before frosting.
For the frosting, sift the 3 cups confectioners' sugar and 3/4 cup cocoa powder together to remove lumps.
Beat 1 stick unsalted butter on medium-high until creamy (about 2 minutes). Reduce speed to low and gradually add the sifted sugar/cocoa mixture alternately with 3–4 tablespoons well-shaken buttermilk. Add 1 teaspoon vanilla and 1/4 teaspoon salt.
Once combined, beat on high for at least 1 minute until light and fluffy. Frost the cooled cupcakes and decorate as desired.