A few things to check:
1) In the console, under Mobile Management Server Settings, Enrollment tab. Click your Site Server, then Edit. Ensure the "Override server connection info" is checked, "Use HTTPS" is checked, and port 443 is specified.
2) On the iOS device that is failing, reset the Symantec agent (Configuration, Apps, Symantec Mobile Managment) and remove any installed profiles (Configuration, General, Profile, MDM Enrollment). Try logging in again. I originally couldn't get iOS 5 to work but I had attempted enrollement prior to installing MR1 (where iOS5 support was added) and it was preventing it from working until I removed the prior enrollment info.
3) Check the SSL certificate on the site server. Are the dates valid? Signed by an authority the agent trusts?
Hope that helps.