I checked out your link but read something disturbing there: "...during non-work hours, they are expected to respond within 3 hours." This, I think, goes totally against my reason to seek freelance work - work on my own time. I'm sorry but Toptal just looks like another company.
You've read the page for prospective clients. We give clients the option to have a developer with that level of responsiveness.
Client and developer arrangements are mutual, and not all clients require developers to respond within 3 hours on their day off. But, if your client does, you need to do it. Moreover, it is just important that you keep your word. If you tell your client you are going away Saturday and won't be able to answer emails, and you cleared this with them up front, there's not going to be any problem. But, if you told your client "Oh hey, don't worry: i'll keep the server running." and then you took off on a vacation without your smartphone and laptop, then that's a problem.
Many clients have had bad experiences with unresponsive developers. At TopTal, we strive to guarantee that they will receive the level of responsiveness desired.
Yup, it mostly boils down to what you seek for. If you seek a complete freedom in your working hours, it might not be a fit for you, but if you seek a steady flow of work, being a member of client's team, with some regular communication involved - Toptal is an organized place to pick up some work without the bidding games happening in elance & odesk.
I'm also a member of the netwokr, picking some work there, some through my own direct contacts. Generally, 'rules of the game' are always agreed with the client, when such rules aren't a fit for both sides, no need to engage in such work, as you wouldn't in the case where you find your own clients. Some are more, some other are less flexible, just like in every other place.