It’s correct that if f and x are expressions, f @@ x is equivalent to f x. But Ok is not an expression by itself, it needs to be always applied to its argument.
In other words, constructor application Ok x is not the same as function application f x, and @@ is a shortcut for the latter.
To paraphrase @emillon’s answer: Ok is a constructor, and constructors are not functions in OCaml, so it cannot be used as an argument to the @@ operator.