Managed to get just about everything working on a fresh install except email notification. Running IIS 6/win2k3 server. PHP5 and mySql (if that matters) 4.something.
From what I've read and seen, I'm under the impression that by turning email on in the Options -> Discussions area I should get emails when folks comment.
Alas. I don't.
The server is running IIS's SMTP server and is known to work (my previous blog used it quite reliably and I've dumped a fake test file through it to make sure nothing is being blocked). Apparently my issue is with PHP and/or WordPress and frankly, after a few hours of googling I'm not sure where to turn.