Abstract: | The o‐substituted hybrid phenylphosphines, PPh2(o‐C6H4NH2) and PPh2(o‐C6H4OH), could be deprotonated with LDA or n‐BuLi to yield PPh2(o‐C6H4NHLi) and PPh2(o‐C6H4OLi), respectively. When added to a solution of (η5‐C5H5)Fe(CO)2I at room temperature, these two lithiated reagents produce a chelated neutral complex 1 (η5‐C5H5)Fe(CO)C(O)NH(o‐C6H4)PPh2‐C,P‐η2] for the former and mainly a zwitterionic complex 2 , (η5‐C5H5)Fe+(CO)2PPh2(o‐C6H4O?)] for the latter. Complex 1 could easily be protonated and then decarbonylated to give 4 (η5‐C5H5)Fe(CO){NH2(o‐C6H4)PPh2‐N,P‐η2}+]. Complexes 1 and 4‐I have been crystallographically characterized with X‐ray diffraction. |