(disclaimer - founder of Puppet)

We at Puppet Labs have always focused on building tools that anyone can use, not just the best hackers in the world. We've got some of the best sysadmins working with us, but we punish them by making them write software that even people who aren't the best sysadmins can use.

So yeah, we get a ton of enterprise adoption as a result, but we've also got a ton of web companies using Puppet. It's true that in the Rails web startup, we're not always the number 1 choice, though. :)