Yeah, I always thought Mustang would be more likely than Marcoh because the old man's grown used to losing people, not to mention he isn't really close to anyone to actually open the gate. Additionally, he even has the technique that works perfectly against Homunculi, that being the anti-philosopher-stone transmutation. They needed someone younger and more willing to open the gate to save someone close to him. Mustang fit the bill really nicely.
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