Re: Highest Ranking Woman?
Since you asked for "the highest ranking woman in TOS" and not "the highest ranking (female) Starfleet officer" I´d go with the Romulan Commander in Enterprise Incident
: she didn´t just command her own ship, but the whole task force.
"Do you give me attitude, Spock?" - "I´m expressing multiple attitudes simultaneously, Sir. To which are you referring?"