The 300TD is priced a bit high for having that many miles and rust, and it is VERY unlikely that the owner is actually getting 30+ MPG. 28 seems to be the top that you can expect unless you drive very conservatively and have a lot of downhill trips and tail winds

Do you mean 300D with a turbo, or 300TD (which is a wagon)?
That is a plus that the timing chain has been replaced though - it is one of the few potential problems that an engine with that mileage would have, may justify the price assuming other things are good and the rust isn't too bad.
I just got a 240D with a 4-speed manual, and as a relatively new manual driver (I have driven stick a little before to learn how and give it a try, but never owned a manual car), I can tell you that it requires more attention to driving, shifting, and traffic than the other manual car I have driven (early 90's toyota). However, if you have got some nice flat parking lots around to learn on, I'd go for it. The price isn't outrageous, considering the mileage and the fact that it has been garaged, also assuming the rust isn't too bad.
If you live in a busy city, the 240d might be a little much to start with, but on the other hand, it could make your kid a more skilled and attentive driver if he starts out on it.
In general both of those prices are ok, but you may be able to find some similar examples for cheaper if you wait around.
With any mercedes diesel, check how easily it starts cold (especially if you live somewhere with real winters), listen to the idle for how smooth it is, generally inspect for rust, ask about oil consumption, look for leaky fluids, check the oil pressure gauge (should be pinning the meter when accelerating and cold idling, and about 2/3 of the way up when warm idling). On automatics, the transmission can sometimes be a little goofy, but it is often just vacuum issues or other non-fatal problems, but look for smooth firm shifting (firm but not neck breaking).
On wagons, check to make sure the rear is not too bouncy or saggy, as it would indicate a problem with the self leveling suspension, which can be a PIA.
I think there are some threads about what to look for when looking at a 300D. Do some searching and reading threads on this forum and you will find a TON of information.
Otherwise, it is just the normal things you look at with a used car.
Good luck!