I actually prefer a chat room over email. It's logged, with group discussion and it's asynchronous. I don't have to begin a reply and then wait for a response. I just get it out in the room and keep going.
Another thing I like about using a room is the chance to use Hubot (http://hubot.github.com/). It makes for some fun and can also be extended to actually do useful stuff.
If your team as an aversion to IM try to entice them with a room is better because it's not one to one and everyone can see and answer questions and it facilitates group discussion easily and it's asynchronous so it gets out of your way.
We've been using skype chat almost elusively for 3 years. At first, I loved the work flow, but in our case it has devolved into an email replacement for one of our team leads. He daily sends reams of chat messages into the room with the expectation of a synchronous response. Messages routinely get lost in the shuffle. I'm working to get him to use email for these sorts of issues -- status, in progress.
If skype had threaded chat conversations, it would be much more manageable. Until then, I miss gmail... :)
Skype has a pretty awful UI for chats. If you get people set up using a bouncer then it's pretty easy to get persistent conversations over IRC, and then people get to use the client of their choice. Plus it's a lot easier to automate with bots.
Another thing I like about using a room is the chance to use Hubot (http://hubot.github.com/). It makes for some fun and can also be extended to actually do useful stuff.
If your team as an aversion to IM try to entice them with a room is better because it's not one to one and everyone can see and answer questions and it facilitates group discussion easily and it's asynchronous so it gets out of your way.