MIXED-METAL PENTANUCLEAR COMPLEXES OF RUTHENIUM(II,III) CARBOXYLATE AND TETRACYANIDOPLATINATE(II)

Mixed-metal complexes constructed from dinuclear ruthenium(II,III) carboxylates and tetracyanidoplatinate(II), [{Ru2(O2CCH3)4}2Pt(CN)4]·2H2O (1) and [{Ru2{O2CC(CH3)3}4}2Pt(CN)4]·2H2O (2), were synthesized and characterized by elemental analysis and IR and UV-vis spectroscopies. These data are in accordance with the formulation of the PtRu4 pentanuclear complexes with two lantern-type dinuclear Ru2 and Pt(CN)4 units. A broad band at near-IR and a distinctive band at visible region (1088 and 443 nm for 1 and 1090 and 446 nm for 2), which can be ascribed to a (Ru2)→*(Ru2) and a (RuO, Ru2)→*(Ru2) transitions, respectively, were observed in the diffused reflectance spectra. Temperature-dependence of magnetic susceptibilities (4.5-300 K) showed that antiferromagnetic interaction between the two 3/2 spins of the Ru2 units through tetracyanidoplatinate(II) is weak (zJ = −0.1 cm) with zero-field-splitting values of 45 and 65 cm for 1 and 2, respectively.

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