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For anyone buying a domain for a new startup, it's an important, and sometimes terribly expensive choice. This post by Fred Wilson: Finding And Buying A Domain Name is a good start, and is immediately followed by an outstanding comment on why dot com is the only TLD that matters. and continues on to how to negotiate a dot-com name by contacting the domain owner cold.
Here's the deal. The only domain name that matters for your startup is .com. Dotcoms got their name in the 90s because they represent business. Dot-com is the money TLD. Even companies like del.icio.us and bit.ly eventually had to buy their dot-com counterparts. There's just too much mindshare about .com.
What are you doing reading? Hurry and buy the domain you're thinking of before it's gone!