I had similar problems just the other day.  There is some code commented 
out in 
dspace-api/src/main/java/org/dspace/identifier/doi/DataCiteConnector.java 
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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