EARLY & Affordable Transport from Toledo to Madrid Airport?

I just got an e-mail from Vueling airlines informing me that our 3 PM September flight from Madrid to Venice is canceled (for “mechanical reasons”, not sure how they can know that 2 months ahead of time, but that’s a whole other rant), and we're now on the flight that leaves at 7 AM. A few major problems with that, the main one being that we're not staying in Madrid that night, we'll be in Toledo - totally not a problem for a flight leaving in the afternoon, but as the AVE train doesn't run before 9 AM on Saturdays, this is going to be a challenge. I'm trying to figure out some affordable options, since the upside of the earlier flight is that we get a whole day in Venice instead of just the evening, so I’d like to try and find a way to make it work. Anybody know if there's anything like a Shuttle Express that might run directly from Toledo to the airport that would be more affordable? I’d really rather not get stuck taking a 100€ + taxi ride if at all possible! I’ve got a friend in Madrid that we’ll be visiting while we’re there that I’m going to check in with for ideas, as well as the hotel in Toledo – I’m sure we're not the first people who have ever had to catch an early flight from Toledo. What are the chances that I can complain to the airline and get them to cover additional transportation costs (I’m guessing very low)?