Complexes of cis-bis(triphenylphosphine)ruthenium(II) with N,S-donor thiobenzhydrazones of polycyclic aromatic aldehydes: Synthesis, properties and structures

Abstract

Reactions of [Ru(PPh3)3Cl2], H2Ln (polycyclic aromatic aldehyde thiobenzhydrazones ArCHNNHC(S)Ph, n=1–4 for Ar=1-naphthalenyl, 9-anthracenyl, 9-phenanthryl and 1-pyrenyl, respectively) and NaOAc in 1:2:2mol ratio in methanol produces ruthenium(II) complexes of formula cis-[Ru(PPh3)2(HLn)2] (1–4) in ∼80% yields. Microanalysis (CHN), magnetic susceptibility, solution conductivity, spectroscopic (IR, UV–Vis, NMR and fluorescence) and cyclic voltammetric measurements have been used for the characterization of 1–4. The complexes are non-electrolytic and diamagnetic. In the electronic spectra, the complexes display multiple absorptions within 505–245nm due to metal-to-ligand charge transfer and ligand centred transitions. The emission spectral features of 1–4 indicate ligand centred emissive states. Molecular structures of 3 and 4 have been determined by X-ray crystallography. In each of 3 and 4, two thioamidate-N,S coordinating (HLn)− and two mutually cis oriented PPh3 molecules assemble a distorted octahedral N2S2P2 coordination sphere around the metal centre. Cyclic voltammograms of 1–4 show an oxidation response within E1/2=0.76–0.86V (ΔEp=90–100mV) versus Ag/AgCl.