XMLRPC is always enabled here at wordpress.COM so that is not the problem.
Support for the iOS app is handled at a separate website: http://ios.forums.wordpress.org/ . Head over there and look through what is there and you might find your answer. If not, post your question there. I have the app installed on my iPhone, but it set up and connected right away and so I’ve little to offer in the way of help.
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