Aluminum surface-bound alkoxyzirconium complexes undergo smooth ligand metathesis reactions with a variety of phenols to give the corresponding surface-bound phenoxyzirconium complex species. This process enables rapid preparation of members of a family of surface-bound complexes which are synthesized in situ from an easy-to-prepare common precursor, Ligand metathesis can be monitored by infrared spectroscopy under ambient conditions or by a combination of infrared and X-ray photoelectron spectroscopic techniques in ultrahigh vacuum.