I had the same problem with my LibreOffice 4 version.

The solution was to reassign the ownership of the directory ".config".

kingpommes@Karlsruhe:~$ sudo chown -hR kingpommes .config

My guess is that my userID changed after I reinstalled my ubuntu some
time ago. So although I used the same user name "kingpommes" in the new
installation, the userID in the probably changed.

Anyway, the command I mentioned above solved the access problem of
LibreOffice.

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https://bugs.launchpad.net/bugs/792947

Title:
  The application cannot be started.  A general error occurred while
  accessing your central configuration.

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