Renfe doesn't show me the train that DB Bahn does

It looks like you might have to do it with multiple transactions: Toledo-Madrid, Madrid-Pamplona, Pamplona-San Sebastian. Apparently the RENFE site is only listing the fastest trips.

The Renfe site should be more accurate since it is their system. Since there is no through train from Toledo to San Sebastian, you have to make 2 reservations for each leg.

I searched Renfe and found the San Sebastian train leaving Camartin at 8:00. That is the other Madrid station; coming from Toledo brings you into Atocha.

Your timeframe to transfer is very tight. It could easily take 20 minutes to go between stations (using the express train - free since you are coming into Madrid by train). Then you have to find your platform and go through security.

Can you get an earlier train into Madrid? That's your best bet.

Following Jeff's suggestion, I did try querying the Renfe site with each of these as separate legs (Madrid-Pamplona and Pamplona-San Sebastian). The good news is that I now see all the segments that DB presented. The bad (?) news is that I have to buy these as 3 individual tickets.

If I go Toledo-Madrid-Pamplona-SanSebastian so that Madrid is all at Atocha, the Madrid connection time is only 15 minutes. Is that too tight? Can I count on the train's arrival time?

The connection in Pamplona is 44 minutes. That sounds doable, yes?

It now looks like the journey that Renfe proposed would be better (cheaper, no connection after Madrid) but, yes, the arrival at 7:20 (Atocha) and 8:00 departure (Chamartin) looks too risky.

I really don't have an option for an earlier train from Toledo - the first one is 6:50am (arriving Madrid-Atocha at 7:20am). Maybe a bus??

A 15 minute connection at Atocha is pretty tight. It's a big station. Even if the train is on time, you have to get off, walk up the platform, find your new platform, go through security and be on board a few minutes prior to departure. Renfe requires passing through security (far less hassle and time than airports but can still take a few minutes) and requires passengers to be onboard a few minutes before departure. And if your Toledo train is even just a few minutes late???

You could try it but what would be your backup plan if you miss the train?

There is a bus that takes about the same time as the train - about 6 hours - and costs about E32. You can find the details and schedules here:
http://www.alsa.es/portal/site/Alsa

Keri, I've been able to buy train tickets from DB with no problem. they'll even mail them to you, and fast too.

Douglas, I agree those connections were WAAAAY too close for my comfort. I've now figured out that the Renfe site doesn't show connecting journeys but I can use DB to query & identify legs. At this point I have found a 4 leg journey (Toledo-Madrid-Zaragoza-Vitoria-San Sebastian). Madrid still involves 2 stations but the time gap is now 1 hr 10 minutes which I am hoping is adequate to get from Atocha to Chamartin. The tightest connection is now the 16 minutes at Vitoria, with a second train 45 minutes later as a backup. (If I buy the Renfe ticket and miss that connection will they honor the ticket I've purchased on the later train?)

Jeff, That bus option looks REALLY good ... but we have concerns about 6 hrs on a bus with no 'facilities' - do you know what kind of bathroom provisions they make?

Charlie, Really? You can get DB to sell you a Renfe ticket? On my search results page it indicates that I cannot purchase the ticket I'm looking at. Hmmm....

The hour plus layover time in Madrid is more than enough. I wouldn't worry about only 16 minutes at Vitoria - it's likely a small station and will only take you a few minutes to go to the other platform. Plus the backup in 45 minutes gives you peace of mind.

For me, 6 hours is a long bus ride. The train will be far more comfortable. The bus will have a WC or will stop, but if you think train WC's are small and icky...

Keri -
The ALSA itinerary shows a 15 minute stop in Burgos which is about 3 hrs into the trip. There may be other stops because bus drivers are people, too. :)

I want to thank everyone for their excellent ideas. Sometimes The Plan reaches a point of complication that suggests it wasn't meant to be. We decided that it would be easier to extend our stay in Madrid by two days and do a day-trip to Toledo. That gets us back to the simple, direct train into SS. Knowing what we know now -- and after checking out Madrid 'on the ground' this year -- we will be better equipped for future years.

Oh, and for the 'Mac' people who are needing to book on the Renfe site (and have read that it is fussy about anything other than I.E. under Windows), I can report that I was able to complete a booking using FireFox.