The page at http://wiki.debuntu.org/wiki/OpenSSL#Retrieving_certificate_informations lists the command lines for that (and printing out the relevant information). From that page and some of the man pages, it seems like what you want is (for bash):
openssl s_client -connect <host>:<port> < /dev/null 2>/dev/null | openssl x509 -fingerprint -noout -in /dev/stdin
If you want the whole certificate, leave off the |
symbol and everything after it.