Everyone is posting about getting ldaps:// working in a WAMP/AD stack, I had a tough time finding how to get it going in RHEL 5.1 (w/ all stock rpms). Good old strace did the trick and helped me find the problem...
Turns out php was looking for the CA file in /etc/pki/CA, and I didn't have the correct permissions on the folder. chmod'ing it to 755 solved my "Can't contact LDAP server" message.