I want to highlight the selected NSToolbarItem like e.g. in Adium (see screenshot).
NSToolbarItem
highlight http://a2.s3.p.quickshareit.com/files/screenshot_b28b67ba9
If you made your toolbar in Interface Builder, you can click on the individual NSToolbarItems and check the Selectable box in the Inspector for the ones you want to have that look. No code needed.