In trouble shooting this we noticed that different extesnion where enabled / disabled when accessing the extension manager from the Commands -> Manage extensions menu in Dreamweaver versus opening the extension manager from the start menu.
An extension that was enabled using the Commands -> Manage extensions menu in Dreamweaver would show in the toolbar, however an extesnion enabled using the start menu would not.
I recommended always accessing the extesnion manager using the commands menu, And contacting Adobe support to troubleshoot why there where multiple Configuration profiles.