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/usr/share/irssi/help/xmppconnect is in irssi-plugin-xmpp 0.53-1+b1.

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XMPPCONNECT %|[-ssl] [-host <host>] [-port <port>] <jid>[/<resource] [<password>]

     -ssl: use SSL when connecting (deprecated, StartTLS will be used by default if this parameter is not specified)
     -host: the host
     -port: the port (if not specified, 5222 is used for a normal connection or 5223 for an SSL connection)

This command makes irssi to connect to specified XMPP account. Current connections are kept and a new one is created.

See also: XMPPSERVER, SERVER, DISCONNECT, RMRECONNS