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In a large bowl, whisk together ¼ cup of olive oil, vinegar, and mustard. Add chicken pieces and toss to coat. Cover and refrigerate for 30 minutes or up to 4 hours.
Preheat the oven to 425°. Heat a large oven-safe skillet over medium-high heat. Shake off excess marinade from chicken and season all over with salt and pepper. Add to hot pan presentation-side-down, and cook until seared and golden, about 6 minutes. Flip chicken and cook until seared on the other side, about 6 minutes.
Scatter zucchini and tomatoes around the chicken and drizzle with remaining olive oil. Season vegetables with salt and pepper, then transfer skillet to oven and bake until a thermometer inserted into the thickest part of the chicken reaches an internal temperature of 165°, about 15 minutes more. Garnish with Parmesan and basil before serving.
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