I had similar problems just the other day.  There is some code commented 
out in 
which will log details of the document being sent at DEBUG level.  You 
could uncomment that code, rebuild, update, and tweak 
config/log4j.properties to set 
log4j.logger.org.dspace.identifier.doi.DataCiteConnector = DEBUG

A simpler way, if you're comfortable with network troubleshooting tools, 
would be to capture the exchange with host mds.datacite.org using something 
like tcpdump or Wireshark.  (Probably this is what I should have done.)

org.dspace.identifier.DataCiteXMLCreator can be run via 'bin/dspace dsrun' 
to show what that code would produce, but it may not be precisely the same 
document.  I didn't learn anything from using it, but that may be because I 
hadn't figured out what to look for until I had given up on it and switched 
to using the debug code noted above.

I don't know of anything built-in that one could just turn on to dump the 
live exchange.  I think I will work up and submit a patch to permanently 
uncomment the debug code in DataCiteConnector.

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