There is always a non-zero chance that a rocket will explode when launched. The early ~~Saturn V~~ pre-Mercury rockets, the Space Shuttle, and new SpaceX rockets all have had numerous explosions during launch or re-entry.
If a nuclear powered rocket were to explode, it would spread nuclear material over a very large area – an incredibly large area if that explosion happens high in the atmosphere. This would be a catastrophic event, and even at low probability of occurrence it is a significant enough danger to make nuclear propulsion a bad idea.
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