Just added a driver to the alpha-property of an material. The Driver works fine, but the property is still "gray" and not as usually "purple", when it is connected to a driver. I appended a simple example, in which the alpha-property of the material is driven. It still shows the default state.
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Here's the reason: Material drivers are currently being inserted in the "anim data" for objects, this to ensure a proper handling with animation dependency order (which is object based). If you insert a "key frame" you can see it's being added to the Material itself.
The UI does a quick lookup on a button draw if the button is animated, but it for this case the test fails.
it's not a trivial fix really, and certainly not something to do quickly. I've marked it on our todo list for future reference. It should definitely be implemented.
http://wiki.blender.org/index.php/Dev:2.5/Source/Development/Todo/UserInterface#UI_Widgets