Heterometallic Palladium(II)–Indium(III) and −Gallium(III) Acetate-Bridged Complexes: Synthesis, Structure, and Catalytic Performance in Homogeneous Alkyne and Alkene Hydrogenation

Abstract

The reaction of Pd(OOCMe) with indium(III) and gallium(III) acetates was studied to prepare new Pd-based heterometallic carboxylate complexes with group 13 metals. The heterometallic palladium(II)-indium(III) acetate-bridged complexes Pd(OOCMe)In(OOCMe) (1) and Pd(OOCMe)In(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 Pd(OOCMe) 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 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.

Pd-based bimetallic catalysts for parahydrogen-induced polarization in heterogeneous hydrogenations

“…For preparation of the Pd-In/Al 2 O 3 catalyst, an aqueous solution of binuclear acetate complex Pd(OOCMe) 4 In(OOCMe) was used as a precursor. The preparation procedure of this complex is described elsewhere (Stolarov et al, 2018). To obtain the impregnating solution, 0.164 g of Pd(OOCMe) 4 In(OOCMe) was dissolved in 4.75 mL of distilled water.…”

“…This, however, does not exhaust the list of activities that would benefit from the facile production/enrichment of NSIMs of polyatomic molecules. In modern science, of significant interest are the properties of NSIMs, including their interconversion processes (Chapovsky and Hermans, 1999) and NSIM behavior upon phase transitions (Curl et al, 1966;Hama et al, 2018); the NSIM-related selection rules in molecular spectroscopy (Kanamori et al, 2017;Ozier et al, 1970) and upon chemical transformations (Hu et al, 2020;Kilaj et al, 2018;Oka, 2004); NSIMs in astrophysics and astrochemistry research (Hama and Watanabe, 2013;Hily-Blant et al, 2018;Shinnaka et al, 2016;Tielens, 2013); and more.…”

Square-Planar Pt(II) and Ir(I) Complexes as the Lewis Bases: Donor–Acceptor Adducts with Group 13 Trihalides and Trihydrides

“…36 Very recently, the structure and catalytic activity of Pd(II)−In(III) and Pd(II)−Ga(III) acetate-bridged complexes was determined experimentally. 37 We may hypothesize that GaCl 3 interactions with cisplatin play some role also in vivo since GaCl 3 was proposed to improve efficacy and to lower toxicity of a combined anticancer treatment of cisplatin and etoposide. 38 Studies dealing with interactions of metal complexes with free unbridged Lewis acids are still rare.…”

Highly-Ordered PdIn Intermetallic Nanostructures Obtained from Heterobimetallic Acetate Complex: Formation and Catalytic Properties in Diphenylacetylene Hydrogenation

“…A convenient way to synthesize supported PdIn IMCs with a pre-defined stoichiometry is to use heterometallic PdIn acetate complex as an IMC precursor [ 28 ]. Originally, two metal components are linked together within initial complex structure by strong acetate bridges, thus ensuring intimate bonding of both metals during metal loading and providing uniform stoichiometry of IMC nanoparticles in a final catalyst.…”