Andy,
Have you cleared your user profile and allowed it to rebuild?
https://wiki.documentfoundation.org/UserProfile
That really is the first step.
Otherwise, seems like a problem with the registered temp folder.
Here is a clip of a correctly configured Tools -> Options -> Paths panel for
LO 5.1.0 (would be same on Vista, 7, 8, 8.1 and 10).
<http://nabble.documentfoundation.org/file/n4173085/LO_ToolsOptionsPaths_Windows7-10.png>
If clearing your user profile does not resolve--Next step is to do a
complete uninstallation, and clean install.
1. Remove (or rename) all of the LO User profile's, e.g.
C:\Users\<usernames>\AppData\Roaming\LibreOffice
2. Login as an administrator's group member, and uninstall LibreOffice.
3. Clean the Windows registry:
HKEY_LOCAL_MACHINE\SOFTWARE\The Document Foundation
HKEY_CURRENT_USER\SOFTWARE\The Document Foundation (for all users)
4. launch a command prompt, change directory to your download, and with CLI
issue command "msiexec.exe /i LibreOffice_4.4.7.2_Win_x86.msi /L*v
installLog.txt" This will log the installation should there still be
issues.
5. Log out and back in as your user. Launch LibreOffice to check if that
resolved the path issues.
Stuart