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Electrochemical, spectroscopic and EPR study of transition metal complexes of dipyrido3,2-a:2',3'-cphenazine

, , , , and . Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1999)

Abstract

The electronic structures of Ru(dppz)32+ and (dppz)MLn, MLn = Ru(bpy)22+, Os(phen)22+, Cu(PPh3)2+, Re(CO)3Cl, Mo(CO)4, PtPh2 or Pt(Mes)2 (Mes = 2,4,6-trimethylphenyl), were compared, based on cyclic voltammetry and spectroscopic studies (UV/visible, EPR of paramagnetic states). According to all exptl. evidence, the lowest lying p* orbital of dppz which is singly occupied in complexes of the dppz radical anion is localized almost exclusively in the phenazine part of the ligand. Among the consequences of this situation are a very weak coupling of the 1st three redn. processes of Ru(dppz)3n, very little difference in the redn. potentials and in the EPR spectra of the radical complexes (dppz.bul.-)MLn, absorption spectra with the intense MLCT transitions to higher lying a-diimine orbitals. on SciFinder(R)

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