You ought to be aware of this:
Personal folder files are unsupported over a LAN or over a WAN link
If you go that route, make sure you keep .pst file backups (and often).
I used to work that way - never suffered a .pst corruption but I used to get the .pst file left locked if Outlook crashed or had to be killed (it used to hang occasionally). To clear the locks I had to restart samba on the NAS.
I now use IMAP (and Thunderbird - but that's a different story).