Reversibly Reduciblecis-Dichloroplatinum(II) andcis-Dichloropalladium(II) Complexes of Bis(1-methylimidazol-2-yl)glyoxal

Abstract

Complexes cis-MCl2(big), big=bis(1-methylimidazol-2-yl)glyoxal, M=Pt, Pd, were prepared and characterized through electrochemistry, spectroscopy, and for M=Pt, by X-ray structure analysis. The seven-membered chelate ring formed through N,N' coordination of the ligand big shows a boat conformation in agreement with density functional theory (DFT) calculation results. No significant intermolecular interactions were observed for the platinum compound. Both the PdII and PtII complexes undergo reversible one-electron reduction in CH2Cl2/ 0.1 M Bu4NPF6; the reduced palladium compound disintegrates above -30 degrees C. Electron paramagnetic resonance (EPR), UV-vis, and IR spectroelectrochemistry studies were employed to study the monoanions. The anion radical complex [cis-PtCl2(big)]*- exhibits a well-resolved EPR spectrum with small but well-detectable g anisotropy and an isotropic 195Pt hyperfine coupling of 12.2 G. DFT calculations confirm the spin concentration in the alpha-semidione part of the radical complex with small delocalization to the bis(imidazolyl)metal section. The results show that EPR and electroactive moieties can be linked to the cis-dichloroplatinum(II) group via imidazole coordination.