The problem seems to be that the Mime definitions in application/config/mimes.php are hideously limited for "pdf".
Look for the line
‘pdf’ => array(‘application/pdf’, ‘application/x-pdf’)
I changed this to
array('application/pdf', 'application/x-pdf', 'application/x-download','application/x-download', 'binary/octet-stream', 'application/unknown', 'application/force-download', 'application/octetstream')
I'm sure there's a million other variations on a theme but this at least got me started with open office 3 (mac version) pdf exports.