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Venice to Rome via Tuscany

My family of four will be traveling from Venice to Tuscany (near Siena) to Rome. I originally thought we would train to Chiusi or Orvieto - get and return car to that location - and then train to Rome. After looking at maps, I am inclined to drive from Venice to Siena area (only 3.5 hours). Then drive from Siena area to Rome via the coast so that we can come into Fiumicino from the "back way." We will be dropping car and then heading into the city. This plans saves time and dollars on train. Questions:
Does overall plan make sense or am I missing a big something? (!)
Where is the best place to pick up a rental car in Venice after staying in central city - airport, train station?
What is the easiest place to drop a car near Rome - the airport or other?
Many thanks in advance for your insights.

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