The key part of your first error reponse is this: [...]into a store expression
.
If you parse the guid first and store in a var, I think it should work:
var guid = Guid.Parse("adsfasd654asdf816asdf");
IsAdmin = db.yaf_prov_RoleMembership
.Any(rm => rm.UserID == UserKey && rm.RoleID == guid );
Whenever you do operations that the 'thing' that executes your LINQ queries does not know how to handle, you'll get this error. In this case, it's entity framework not knowing how to translate Guid.Parse into an SQL statement/ 'store expression'.
EDIT: Modified to use .Any
. as per Sergey Berezovskiy's answer