There are many. Two big ones are Alpha and PA-RISC. NetBSD and Linux continue to support both. Linux distro choices are pretty much limited to Gentoo though.
2. LLVM does not support as many backends as GCC does, so even if you did get 100% of the LLVM supported backends up and running, you'd still be missing some.
But even for the architecture part there can be differences. For example, my understanding is that a lot of the calling convention details need to be handled by the frontend in LLVM, leading rustc to duplicate logic from clang here. Things like varargs FFI with C code can be particularly gnarly.