Synthesis and structural characterization of a simple Cu(I) and an unexpected mixed-valence copper(I/II) complex with a supporting phosphinoferrocene amine ligand

1'-(Aminomethyl)-1-(diphenylphosphino)ferrocene (1) reacts with [Cu(MeCN)4][BE] in a 2:1 molar ratio to afford the chelate complex [Cu(1-kappa N-2,P)(2)][BE] (2). A similar reaction of 1 with copper(I) chloride furnished an unexpected mixed -valence Cu(l)/Cu(II) octacopper complex, [Cu-4(mu(P,N)-1)(2)(mu-Cl)(5)Cl(1H-kappa P)(2)(t-Cl)(5)Cl(1HO)(H2O)](2) (3), comprising P,N-coordinated 1 and chloride ions as the bridging ligands, and N-protonated phosphinoamine 1H(+) as a monodentate phosphine donor. The structures of 2.AcOEt and 3.10CHCl(3) were determined by single-crystal X-ray diffraction analysis, and the redox behavior of 2 was examined by voltammetric techniques. 2016 Elsevier B.V. All rights reserved.