Preparation of Functionalized p-Phenylenediamine Derivatives Using Arene−Iron Chemistry

Selective displacement of chloride from cyclopentadienyl(1,4-dichlorobenzene)iron(1+) by a series of cyclic secondary amine nucleophiles is described. This selectivity, in combination with further manipulation of the complexes, allows access to a series of unsymmetrical and/or functionalized tetraalkyl- p -phenylenediamine complexes. A series of demetalated phenylenediamines were shown by CV to have redox potentials distributed over a range of 320 mV, as a consequence of remote functionality. Preliminary fluorescence studies on a series of electron acceptor-substituted phenylenediamines indicated quenching of the phenylenediamine fluorescence, attributable to rapid electron transfer.