Cleavage of the dimeric heterometallic complexes [Pd(dppf)(μ-Cl)]2[BArF24]2 (dppf = 1,1′-bis(diphenylphosphino)ferrocene, BArF24 = tetrakis(bis-3,5-trifluoromethylphenyl)borate) via addition of monodentate phosphine ligands

Abstract

The cleavage of the heterometallic, chloro-bridged dimer [Pd2(dppf)2(µ-Cl)2][BArF24]2 (dppf = 1,1′-bis(diphenylphosphino)ferrocene; BArF24 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) was of interest within this study. The addition of the monodentate phosphines, PPh3, PMe3 and diphenylferrocenylphosphine (PPh2Fc), resulted in the formation of three new [Pd(dppf)(PR3)Cl][BArF24] complexes. These new compounds were characterized by NMR and the X-ray crystal structures of all three compounds were obtained. Structural parameters for these compounds were compared to other square-planar Pd(II) compounds with a dppf ligand. In addition, the oxidative electrochemistry of these three compounds was examined using cyclic voltammetry and the electronic communication between the two different iron centers in [Pd(dppf)(PPh2Fc)Cl][BArF24] was explored.