What you want is this:
Microsoft Knowledge Based Article 223188
Change the System/Boot Drive Letter
Log on as an Administrator.
Start Regedt32.exe.
Go to the following registry key:
HKEY_LOCAL_MACHINE\SYSTEM\MountedDevices
Click MountedDevices.
On the Security menu, click Permissions.
Verify that Administrators have full control. Change this back when you are finished with these steps.
Quit Regedt32.exe, and then start Regedit.exe.
Locate the following registry key:
HKEY_LOCAL_MACHINE\SYSTEM\MountedDevices
Find the drive letter you want to change to (new). Look for "\DosDevices\C:".
Right-click \DosDevices\C:, and then click Rename.
Note You must use Regedit instead of Regedt32 to rename this registry key.
Rename it to an unused drive letter "\DosDevices\Z:".
This frees up drive letter C.
Find the drive letter you want changed. Look for "\DosDevices\D:".
Right-click \DosDevices\D:, and then click Rename.
Rename it to the appropriate (new) drive letter "\DosDevices\C:".
Click the value for \DosDevices\Z:, click Rename, and then name it back to "\DosDevices\D:".
Quit Regedit, and then start Regedt32.
Change the permissions back to the previous setting for Administrators (this should probably be Read Only).
Restart the computer.
PS: Ive had to use this once or twice so I know that it works