RESUMO
The reaction of Pd3(OOCMe)6 with indium(III) and gallium(III) acetates was studied to prepare new PdII-based heterometallic carboxylate complexes with group 13 metals. The heterometallic palladium(II)-indium(III) acetate-bridged complexes Pd(OOCMe)4In(OOCMe) (1) and Pd(OOCMe)4In(OOCMe)·MeCOOH (1a) were synthesized and structurally characterized with X-ray crystallography and extended X-ray absorption fine structure in the solid state and solution. A similar Pd-Ga heterometallic complex formed by the reaction of Pd3(OOCMe)6 with gallium(III) acetate in a dilute acetic acid solution, as evidenced by atmospheric pressure chemical ionization mass and UV-vis spectrometry, was unstable at higher concentrations and in the solid state. Complex 1 catalyzes the liquid-phase-selective phenylacetylene and styrene hydrogenation (1 atm of H2 at 20 °C) in acetic acid, ethyl acetate, and N, N-dimethylformamide solutions, while no Pd metal was formed until alkyne and alkene hydrogenation ceased.
RESUMO
Platinum acetate blue (PAB) of the empirical formula Pt(OOCMe)2.5±0.25, a byproduct in the synthesis of crystalline platinum(II) acetate Pt4(OOCMe)8, is an X-ray amorphous substance containing platinum in the oxidation state between (II) and (III). Typical PAB samples were studied with X-ray diffraction, differential thermal analysis-thermogravimetric, extended X-ray absorption fine structure, scanning electron microscopy, transmission electron microscopy, magnetochemistry, and combined quantum chemical density functional theory-molecular mechanics modeling to reveal the main structural features of the PAB molecular building blocks. The applicability of PAB to the synthesis of platinum complexes was demonstrated by the preparation of the new homo- and heteronuclear complexes Pt(II)(dipy)(OOCMe)2 (1), Pt(II)(µ-OOCMe)4Co(II)(OH2) (2), and Pt(III)2(OOCMe)4(O3SPhMe)2 (3) with the use of PAB as starting material.
