Synthesis and structural characterization of a simple Cu(I) and an unexpected mixed-valence copper(I/II) complex with a supporting phosphinoferrocene amine ligand
2016
Abstract
1'-(Aminomethyl)-1-(diphenylphosphino)ferrocene (1) reacts with [Cu(MeCN)4][BF4] in a 2:1 molar ratio to afford the chelate complex [Cu(1-k2N,P)2][BF4] (2). A similar reaction of 1 with copper(I) chloride furnished an unexpected mixed -valence Cu(l)/Cu(II) octacopper complex, [Cu4(mu(P,N)-1)2(mu-Cl)5Cl(1H-kP)2C)(5)(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 3.10CHCl3 were determined by single-crystal X-ray diffraction analysis, and the redox behavior of 2 was examined by voltammetric techniques.