First try this: Close Outlook, click Start->Run, type Outlook /cleanprofile
If that doesn't do the trick then recreate the Outlook profile. Profile corruption is the source of many strange behaviours in Outlook.
You may first want to save away the address cache (the .nk2 file) which contains the addresses the user has prevoiusly sent successfully. You find the .nk2 file here (XP):
C:\Documents and Settings\<user>\Application Data\Microsoft\Outlook
(Vista / W7: C:\Users\{username}\AppDat
a\Roaming\
Microsoft\
Outlook)
If you do not know how to recreate a profile:
http://www.howto-outlook.com/faq/newprofile.htmAfter recreating the profile you can restore the .nk2 file to the same location assuming you used the same name for the new Outlook profile.