Actually the documentation about escape sequences in PHP is wrong. When you use \xc2\xa0 syntax, it searches for UTF-8 character. But with \x{c2a0} syntax, it tries to convert the Unicode sequence to UTF-8 encoded character.
A non breaking space is U+00A0 (Unicode) but encoded as C2A0 in UTF-8. So if you try with the pattern ~\x{00a0}~siu, it will work as expected.