Some of these options only work with boundaries (edges) of a 3D object. Make sure the edge is selected instead of a face.
Take this circular shape for example. The 5 options in the left tab are disabled as the only a face is selected.
3 options are now enabled which allow you to extrude, copy or pivot an edge.
Try pulling this shape to a cylinder and select the circumference; the round, chamfer, etc. All 5 operations will be automatically enabled, now allowing you to round & chamfer edges.