Thanks all.
Unix for the win, once again!
Here's what I ended up with....
1. using Automator, create an app ('BU_PS' or 'BU_LR') that executes a shell script.
2. The shell script contains the magic incantation 'open -W <path to application>'
Normally, the open command on Mac's executes in the background and immediately return but w/ -W it 'waits' (ie. foreground)
3. When the app in question does exit, the shell script finally continues and mounts the needed volume and either does some rsync magic or will run an applescript via osascript command (needed to script Chronosync which I'm considering buying)
John, there isn't IMO a problem other than that my NAS was slow as molasses and since all the images are there, it's even worse when I 'Edit in Photoshop' which forces what can be multi-hundred MB .psd/.tiff over to the NAS where I can get a cup of coffee. So after considering the options & costs and probable performance gains over single GigE, I settled on installing a spare disk I had into my machine and moved all the images over to it while keeping the RAID1 intact as backup (which is then backed to 2 different disks).
I strongly considered building my own NAS (NAS4Free/FreeNAS) but that would have been $600-900 (and for a moment considered 10gE till I saw the cost ($900 just for the 2 cards) and gotten me some performance gain but not as much as simply adding a $0 disk and some scripting.
I'm only exposed to single disk failure during the time that LR or PS is open which I can accept w/o more heroics.