The one reason I can think of is to prevent implicit conversions being applied to the thing being cast. In your example, if you said:
bool( "foo" );
then “foo” would be implicitly converted to a string, which would then have the explicit bool conversion you provided applied to it.
This is not possible if the bool operator is a member function, as implicit conversions are not applied to *this. This greatly reduces the possibilities for ambiguity – ambiguities normally being seen as a “bad thing”.