Perhaps:
mm = {a, b};
Assuming[i == 1 || i == 2,
FullSimplify[Reduce[{Or[mm[[i]] == a, mm[[i]] == b], $Assumptions}]]
]
Or:
mm = {a, b};
Assuming[i == 1 || i == 2,
FullSimplify[
Reduce[Quiet[{Or[mm[[i]] == a,
mm[[i]] == b], $Assumptions}, {Part::pkspec1}]]]
]