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Is there any reason why I can't add a 2003 Server to a domain as DC when the existing, and only Domain Controller is a 2000 server?
Nope, Windows 2003 Server is fully compatible with Windows 2000 Server domains. There should not be a problem. If there is, then it is either a network hardware issue, a TCP/IP config issue, or your Windows 2000 Server has become corrupted.