In talking with a lot of people who work with both Silverlight and WPF, even those who are excited about Silverlight and push for it strongly, I hear a lot of the say fairly emphatically that if you are going to be developing exclusively for a full-trust Windows environment, WPF is hands-down the obvious choice.
That's not to say that Silverlight is an inferior product or that there aren't times will Silverlight will be the clear winner. But when you say "I'll be deploying LOB apps on a corporate network running only windows computers," it sounds like WPF is the clear winnder.
You could decide to go down the Silverlight route in anticipation of all of the great new OOB feature os SL4. I've even heard rumors that SL and WPF will eventually merge, so it may not even really matter, right? Well, I think what you'll find if you go with Silverlight is that some of the advanced features that you thought were there weren't there in the way you expected. For example, SL4 will be able to run in "Elevated Trust" (not full trust) and you might find this limiting at a frustrating point in the project where a lot of your code base is already in Silverlight.
Certainly keep your eyes on Silverlight, but for your current business case, WPF will likely be the best fit.