Oxygenation and carbonylation studies of some ruthenium(III) Schiff base complexes containing nitrogen and oxygen as donor atoms. II

Taqui Khan, M. M. ; Khan, N. H. ; Kureshy, R. I. ; Boricha, A. B. (1990) Oxygenation and carbonylation studies of some ruthenium(III) Schiff base complexes containing nitrogen and oxygen as donor atoms. II Inorganica Chimica Acta, 174 (2). pp. 175-184. ISSN 0020-1693

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Official URL: http://www.sciencedirect.com/science/article/pii/S...

Related URL: http://dx.doi.org/10.1016/S0020-1693(00)80297-2

Abstract

Synthesis and characterization of a series of ruthenium(III) Schiff base complexes of the type [RuIIILXY] where L=Schiff base viz. bis(naphthaldehyde)-o-phenylenediimine (naphoph), bis(naphthaldehyde)ethylenediimine (naphen), bis(naphthaldehyde)propylenediimine (naphprop) and bis(naphthaldehyde)diethylenetriimine (naphdien); X=Cl and Y=Cl imidazole (Im) or 2-methylimidazole (2-MeIm) are reported. Elemental analysis, conductivity and IR studies of the complexes suggest an octahedral geometry around ruthenium. Magnetic moments of the complexes indicate a single unpaired electron in a low spin d5 configuration. Oxygenation studies in DMF or THF solutions suggest the reversible binding of molecular oxygen to the ruthenium(III) complexes. EPR studies at liquid nitrogen temperature and UV---Vis measurements at room temperature support the formation of a Ru(IV) superoxo species [RuIVL(O2)Y]. The EPR spectrum of the Ru(IV) superoxo complex at 77 K (g1=2.063, g2=2.047, g3=2.023) is consistent with the odd electron occupying a highly localized antibonding π orbital of molecular oxygen. The reversible binding of O2 and CO has been carried out in DMF at 10, 25 and 40°C. The complexes show discrimination against the binding of CO over O2 as evinced by values of KO2 and KCO in the complexes. The thermodynamic paramegers ΔH°, ΔG° and ΔS° for oxygenation and carbonylation reactions are evaluated.

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