Don't know why Dave deleted his answer - you should just move string parsing out of store expression. Otherwise Entity Framework tries to convert Guid.Parse method call to SQL, and fails to do that:
var adminRoleID = Guid.Parse("adsfasd654asdf816asdf");
Also use Queryable.Any to simplify your query:
IsAdmin = db.yaf_prov_RoleMembership
.Any(rm => rm.UserID == UserKey && rm.RoleID == adminRoleID);