Indeed, so Km=0 would imply K-1=-Kcat.
However, deriving the MM equation at various stages requires us dividing by Km, and so Km must strictly not be zero for the derivation to make sense..
Also if we let Km=S (as we would to find that Km is half Vmax) then the velocity is also undefined.
Hence, i cannot make sense of it mathematically. But does Km=0 make sense physically?