When you reflect a diagonal over a line of symmetry, the diagonal will land perfectly on the other diagonal (and vice versa). This suggests that one diagonal is a mirror copy of the other.
Another way to put it: The vertex points of the rectangle will swap when we reflect over a line of symmetry. A diagonal is simply the opposite vertex points joined together. So this is why the diagonals swap places (because the vertices line up perfectly when you apply the reflection).