I am also having this problem again since the upgrade to 12.10.

I get

Error saving the document <filename>:
Nonexistent file.

then

Error saving the document <filename>:
General Error.
General Input/output error.

then the LibreOffice window cannot be closed via the GUI.

Not sure if this is related, but It seems the "mount" point changed from 
$HOME/.gvfs/<share> to /run/user/$USER/gvfs/<share>.
Save As works for me if I change to a directory under 
/run/user/$USER/gvfs/<share>.

Ubuntu 12.10 x86_64
Version 3.6.2.2 (Build ID: 360m1(Build:2))

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You received this bug notification because you are a member of Desktop
Packages, which is subscribed to libreoffice in Ubuntu.
https://bugs.launchpad.net/bugs/792622

Title:
  [Packaging] Libreoffice should use gnome vfs

Status in “libreoffice” package in Ubuntu:
  Fix Released

Bug description:
  Binary package hint: libreoffice

  I browse to a samba share using nautilus. (in location bar it show the
  folder path as smb://)

  I open a document, edit it and save it: it works.

  I choose export as pdf: it fails with a general error, i/o error.

  I choose save as and just chnage the file name: it fails with a
  general error, i/o error.

  ProblemType: Bug
  DistroRelease: Ubuntu 11.04
  Package: libreoffice (not installed)
  ProcVersionSignature: Ubuntu 2.6.38-8.42-generic 2.6.38.2
  Uname: Linux 2.6.38-8-generic x86_64
  NonfreeKernelModules: nvidia
  Architecture: amd64
  Date: Sat Jun  4 10:14:33 2011
  InstallationMedia: Ubuntu 11.04 "Natty Narwhal" - Release amd64 (20110427.1)
  ProcEnviron:
   LANGUAGE=fr_FR:en
   PATH=(custom, user)
   LANG=fr_FR.UTF-8
   SHELL=/bin/bash
  SourcePackage: libreoffice
  UpgradeStatus: No upgrade log present (probably fresh install)

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