Preheat oven to 350°F / 180°C and line a muffin pan with cupcake liners.
In a large bowl, sift the dry ingredients, including the flour, sugar, cocoa powder, baking powder, baking soda, and salt. (But not the espresso powder). Whisk everything together.
In a separate bowl, combine all the wet ingredients, except the hot water, which includes the eggs, milk, sour cream, vegetable oil and vanilla. Whisk together lightly until it makes a homogeneous mixture.
Pour the wet ingredients into the flour mixture and whisk until everything is combined and there are no lumps. Make sure you scrape the bottom of the bowl.
In a small bowl or a glass, combine the boiling water with the espresso powder and mix until completely dissolved. Pour the hot coffee into the cake batter and mix until combined.
Divide the chocolate batter into the cupcake liners, filling them about ⅔ full. The batter is very liquid, so it may be easiest to pour it in or use a batter dispenser.
Bake for 18-22 minutes or until the cupcakes are springy and a skewer inserted comes out with moist crumbs.
Let the cupcakes sit in the pan for 5-10 minutes before removing to a wire rack to cool.
Make the Chocolate Buttercream
Make sure the butter is completely at room temperature before beginning. It can't be too cold or too warm, or the buttercream won't form properly.
Melt chocolate in the microwave in 30-second increments until totally melted. Set aside.
Whip the butter on medium-high speed for a full 5 minutes. I like to pause every 90 seconds or so to scrape down the sides of the bowl.
Slowly add the condensed milk, drizzling in while it whips. It's important not to rush this step or the buttercream might split - go slowly and gradually.
Once all the condensed milk is incorporated, turn the mixer up to max speed for 1 minute.
Scrape down the sides of the bowl and pour in the melted chocolate, vanilla, and a pinch of salt - continue to whip until incorporated.
The buttercream should be thick and glossy - if it isn't, see the troubleshooting guide in my Russian Buttercream post.
Notes
For best results, I always recommend weighing your ingredients with a kitchen scale, rather than using cup measures. It's very hard to weigh dry ingredients accurately with cup measures, and this is the number one reason I see for people's bakes failing. I always list my recipes in both cups and grams so you can choose what is best for you. Russian buttercream is extremely simple to make, but can be problematic if your butter is not at the right temperature or if the ingredients are added too quickly. If your buttercream doesn't look right, don't worry! We can save it. Check my Russian Buttercream post for a troubleshooting guide on how to fix broken buttercream.