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Preheat oven to 450 degrees and place large rimmed baking sheet inside. Preheating baking sheet helps ingredients cook evenly.
While oven preheats, place broccoli florets and onion in medium bowl. Drizzle with 1 tablespoon oil. Sprinkle with sea salt and pepper and toss to coat. Set aside.
Make rub: In small bowl, combine brown sugar, cumin, chili powder, paprika, garlic powder, sea salt, black pepper, and chipotle powder.
Rub chicken thighs with remaining teaspoon oil. Sprinkle all over with seasoning rub.
When oven is preheated, carefully remove hot sheet pan and coat with olive oil. Spread vegetables in even layer on pan, leaving spaces for chicken thighs. Nestle thighs among vegetables.
Return baking sheet to oven and bake 15 minutes. Stir vegetables and continue cooking 5 minutes more until chicken is cooked through and registers 165℉ on an instant read thermometer.