LW must be configured in your firewalls:
http://www.limewire.com/english/content/firewalls.shtml
Chat should be enabled.
Need to have free upld & downld slots & bandwidth. If either are too busy then you're going to struggle to DC. (Try opening up more upld & downld slots under Tools>Options>....)
How to Direct Connect, Browse & Chat But it's not always easy. Sometimes there's no easy explanation if it doesn't work.