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.
Chung
Min-Chul
MC
Department of Chemical Engineering, Sunchon National University, 315 Maegok-dong, Suncheon, Jeonnam 540-742, Korea.
Ahn
Ho-Geun
HG
Kwak
Chee-Hun
CH
Akita
Munetaka
M
D002412:Cations; D004563:Electrochemistry / Q000379:methods; D004581:Electronics; D004583:Electrons; D007501:Iron / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D053768:Metal Nanoparticles / Q000737:chemistry; D008956:Models, Chemical; D008962:Models, Theoretical; D036103:Nanotechnology / Q000379:methods; D009584:Nitrogen / Q000737:chemistry; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D013816:Thermodynamics
D002412:Cations; D007501:Iron; D009584:Nitrogen