I am planning to develop a complex Node application with 30 modules which will be purely accessed thru REST services - backbone being one of the front-ends. I am not sure if I should use Express or Connect as the application does not use any views.
Express gives you everything in Connect plus:
It sounds like you'd benefit from the routing, configuration, and settings in particular. You might want to look into restify as an alternative.
Express is built on Connect, and exposes many of its features in a more friendly way. The one major thing you'll get from Express is a built-in router (complete with route-specific middleware, error handling, etc); however, if you're comfortable with rolling your own routing solution and don't need the other features offered by Express, you can build on Connect itself.
This post partly answers your question
What is Node.js' Connect, Express and "middleware"?
Now about the REST services in node.js, you may want to read this blog post about building REST APIs using Express. MongoDB and Backbone.
Good luck!