TL;DR: Windows extended paths are messy and annoying. \\?\ is "effectively" ignored (as it (roughly, I don't really understand extended paths) just explicitly states "look for a drive name"), so the PathBuf API skips it for the path introspection API, such that \\?\C:\path behaves the same as C:\path.
//?/C:/path doesn't have this behavior, because it isn't a Windows extended path. (In fact, windows file explorer will try to treat this path as a URI and open it in your browser.)
Thanks for your answer. BTW: \\?\ just tells Windows to break the 260 characters limitation for paths. IMHO this is just a workaround for a broken design.