I developed, and am responsible for, a moderately complex b2b web API that is been in use for about three years. A b2b API embodies a contract between organisations, and it's important to understand that this is different to b2c (e.g. Twitter) which is less restrictive.
The biggest issue for me has been dealing with change. User requirements change. The underlying system changes and accretes new features that need to be exposed in the API. How to deal with this without either compromising the integrity of the API's design or (at the other extreme) breaking systems that use the API, is not easy. I don't know of any easy answers, but design your URLs and data schemas with versioning in mind and get to know the developers who use your API.
Documentation is very important. If your API exposes complex data then make sure that you have good documentation on what every data element means.