Oh, I should mention that I did this on the trunk out of SVN, YMMV.
Solved it!
For some reason, PHP’s mail() function was hanging. I changed line 189 of wp-includes/pluggable.php from:
$phpmailer->IsMail(); // set mailer to use php mail()
to
$phpmailer->IsSendmail(); // set mailer to use sendmail
Of course, I made sure I had a working sendmail first. All good, thanks to everyone that pointed me towards email as the culprit…
Indeed it is. I’ve got other apps successfully using sendmail on this machine.
Any other thoughts?