Electronic coupling in dimetallic complexes with pi-conjugated bridge.

Compound 2, [(eta5-C5Me5) Fe(dppe)]2(mu-C[triple bond]C-CH==CH-C[triple bond]C), was prepared by the reaction of compound 1, [eta5-C5Me5) Fe(dppe)]2+ (mu2-C==CH-CH=CH-HC=C).(PF6)2-, with KOBu(t). Compound 2 showed two quasi-reversible one-electron oxidations at -0.674 and -0.253 V, respectively. The comproportionation constant, Kc, was calculated from these measurements. The mixed-valence(MV) radical cation 2+ showed an absorption peak at 1586 nm, which was assigned to the MV pi-pi band of the delocalized complex (Robin-Day Mixed-valence Class III) and the effective coupling parameter, Hab, is consistent with the presence of electronic delocalization.