I would definitely recommend Butler - see my sig, although it is free for about 6 months or so - until June/July. But it is a wonderful app. I will be buying it when it expires (not really freeware, I know).
VLC is essential, NeoOffice is good, and so is GimpShop, SongBird is worth keeping an eye on, YamiPod is superb for getting files to and from an iPod.