1) How would you go about educating others on a complex piece of
framework?
Answer: I wouldn't focus too much on UML specifics as your audience might get lost. I would suggests taking a look at UML Distilled, Third Edition as it will touch on the most important diagrams you can use, as well as how to use them. As others have said, unit tests (or integration tests if the code doesn't support it), and inline documentation could be very helpful too.
2) Will UML benefit?
Answer: This depends on the audience. Do they already know UML? If so it will likely help. Otherwise, anything but class diagrams and use cases may require you to do double duty (teach the program and UML).
3) What UML tools are there for .net apps?
Answer: I can't speak for anything other than UMLet. Yes, it's a java tool, but it has a standalone version. It makes it fairly easy to create diagrams. I use it instead of a white board for experimenting with designs. However, this tool would require you to manually create everything, which isn't what I think you are wanting. I did a bit of searching and came across StartUML, which is open source. It appears to be able to generate UML from c# code.
4) Can UML tools auto-generate sequence diagrams and at least this
will give more information on how the
objects interact?
Answer: Others have mentioned tools in VS2010 Ultimate and other programs regarding sequence diagrams. But if you don't have that version of the IDE (or want the other programs mentioned), VS2008 PRO can at least generate class diagrams for you, showing how they are related. If you do have VS2010 ultimate, here is an article on it.