This is something that SQL database fans don't get. A small start-up can't afford to have a team of guys fiddling with incredibly obscure performance tuning settings.
A developer might not know how to optimize a slow-running Postgre query, but he knows how to cache data and denormalize in a manner that makes the query he wants to run fast. And a document-store plays nice with this.
Any simple relational beauty of SQL databases falls down once you get over a few million rows, and then the hideous hacks and bizarre settings start coming out. At that point you need a pile of domain-specific knowledge to make them play nice.
Mongo takes the domain-specific knowledge out of the equation and lets the developers apply their existing skill-set to the data.
I've you've got a thousand employees? Get a few DBAs and Postgre.
If you've got, like, five?