Spray the inside of your slow cooker with non-stick spray and have it ready to go.
Before doing anything else, I always recommend doing your mise en place (en français). That's fancy French chef talk for chopping everything and having it all measured and ready to go before starting to cook. No more looking for something and realizing that you don't have it or that it's not ready to go, just do what the French chefs say and put "everything in place" before you start the cooking.
Using a heavy pan, like cast iron or stainless steel, sear all sides of your roast over high heat. Really get a good sear on all the sides. Don't be afraid that you'll overcook it. This is a BIG piece of meat.
Place roast in the bottom of your slow cooker, fat side up.
In the same pan as you seared your roast, add 2 tablespoons of olive oil and heat to medium high. Sauté your vegetables until they begin to soften and get a little color. Add your garlic and sauté another minute. Throw in your thyme, rosemary, and basil and give it a stir. We're using the same pan because we want to keep all those meaty flavors to ourselves. We want the veggies and the meat to be madly in love by the end of this recipe!
In a medium bowl combine your tomatoes, beef broth, tomato paste and red wine vinegar. Using your hands (with gloves, if you want) really squish up those tomatoes and mix everything together. You might be thinking you could have just bought crushed tomatoes. Yeah, you could, but whole San Marzano tomatoes are just peeled tomatoes and juice. Very often crushed tomatoes are a mixture of diced tomatoes and tomato sauce or purée, and not as good quality or flavor. Trust me on this. I wouldn't steer you wrong.
Now pour the tomato mixture all around your roast. Mmm. Already smelling good isn't it?
Finally take all your large chunked vegetables and place them all around your roast. Toss those baby tomatoes right on top. Put on the lid, set it to low and walk away for 8-10 hours. Go to work. Go see a double feature. Take 2 naps.
When you come back, it will look like this! And you will be so happy!