So it was bound to happen at some point. I have over 90 websites setup in dreamweaver and have had an occasional error, but this was a new one on me.
Every time I tried to load Dreamweaver it would get stuck at
Initializing Extension Data
Off to find a solution in search and found this nice little gem that fixed it right up.
I have a similar solution in Dreamweaver CS4 Windows.
The folder in question can be found at /Documents and Settings/[login ID]/Application Data/Adobe/Dreamweaver CS4/[language code]/Configuration/SiteCache.
In my case, I found it sufficient to delete the folder and file for the site I last worked on. When I re-launched Dreamweaver, it automatically rebuilt the cache for just that site.
Source Here
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Great to see it's helping out. Had me stumped at first too.