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This seemed to be a problem at Logitech's end - they sorted it out yesterday and now the PS3 is paired with Remote Buddy and working perfectly.
Thanks for keeping everybody updated!
One question... If I've paired Remote Buddy as a PS3 am I still able to add an actual PS3 to the Harmony Remote or will they conflict? I tried last night and
after adding RB and testing it worked I added my PS3. After testing the PS3 worked, RB was no longer paired with the Harmony Remote (what it thought was the PS BD Remote).
I turned off the PS3, restarted the Harmony Hub and RB worked perfectly again but now the PS3 activity is asking to be paired again...
This may be a regression in Logitech's Hub firmware or they may ship a different Hub hardware by now.
I have been able to pair several Macs as PS3s with the Harmony Hub that came with the Harmony Smart Remote and reliably switch between the Macs in 2014. If it works for multiple Macs, it should also work with a mix of Macs and PS3s. That's only an assumption, though: I don't own a PS3 and could therefore not try this.