Linux Mint as a Debian based version of their distro, which comes with all the desktop polish of Mint, but in their own words: "it's not as stable. Things are likely to break more often but fixes can also come quicker. For this reason, LMDE requires a deeper knowledge and experience with Linux, dpkg and APT"
Personally I'd take a look at OpenSuSE. It was a pretty good as a Just Works desktop last I looked, but that was a few years ago.
Another option is actually PC-BSD. I've never quite gotten along with it, but that is mainly because I want to do all kinds of hacky strangeness, but for a newbie desktop it's solid with great documentation and easy to install software.