Some bits in MS-SQL are somewhat painful... powerful, but painful.. dealing with XML types is particularly nasty. I can't really compare that on PostgreSQL's side... What gets me with MS-SQL is that I can setup and run with very little need for digging into advanced configuration options. Replication is relatively simple, and easy to do (though expensive).
On the other side, having played with PostgreSQL + plv8, it's NICE ... if I could get a full node environment inside PostgreSQL (node modules as function libries), that would be amazing.