Could I sipon some coolant out of the expansion tank first so that I get level down below the thermostat?
You'd empty the expansion tank, but not the cooling system. It does what it says on the tin, provides for expansion of the coolant.
If it were me, I'd clamp the hoses to the expansion tank and heater to preserve their contents, remove the top hose, losing the minimum necessary that way, change the thermostat and then top up afterwards.
Actually I wouldn't. I'd just drain the lot and refill. Life's too short to worry about a few quid's worth of antifreeze.
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