The reaction of Pd-3(OOCMe)(6) with indium(III) and gallium(III) acetates was studied to prepare new Pd-II-based heterometallic carboxylate complexes with group 13 metals. The heterometallic palladium(II)-indium(III) acetate-bridged complexes Pd(OOCMe)(4)In(OOCMe) (1) and Pd(OOCMe)(4)In(OOCMe)center dot 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 Pd-3(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 H-2 at 20 degrees C) in acetic acid, ethyl acetate, and N,N-dimethylformamide solutions, while no Pd metal was formed until alkyne and alkene hydrogenation ceased.