The First Heterometallic Acetate-Bridged Pt(II)–Pd(II) Complex: Synthesis, Structure, and Formation of Bimetallic PtPd2 Nanoparticles
The reaction of platinum acetate blue, empirically described as Pt(OOCMe)2.50, with palladium(II) acetate Pd3(μ-OOCMe)6 gave the first heterometallic acetate-bridged platinum(II) and palladium(II) complex Pd2Pt(μ-OOCMe)6 (I) as co-crystallizates 17Pd2Pt(μ-OOCMe)6 ⋅ 4Pd3(μ-OOCMe)6 ⋅ 42C6H6 (IIa) and 17Pd2Pt(μ-OOCMe)6 ⋅ 4 Pd3(μ-OOCMe)6 (IIb). Single crystal X-ray diffraction (CIF files CCDC nos. 1568105 and 1852744), EXAFS, and quantum chemical studies (DFT and QTAIM) of complex I revealed a slightly distorted triangular structure similar to the structure of palladium(II) acetate Pd3(μ-OOCMe)6 and hypothetical platinum(II) complex Pt3(μ-OOCMe)6. The thermal decomposition of complex IIa gives the bimetallic alloy PtPd2. A combined X-ray diffraction and EXAFS study demonstrated that the obtained material consists of core (Pt)–shell (Pd) particles with an average size of ~28 nm and a minor amount of smaller (~5 nm) PdO nanoparticles on the surface. The obtained results are useful for the understanding of the nature and structure of the supported phase of heterogeneous Pt–Pd catalysts.
Keywords:platinum palladium acetate complexes synthesis X-ray diffraction crystal chemistry quantum chemical analysis nanoparticles
X-ray spectroscopy studies (XANES and EXAFS) and quantum chemical calculations were supported by the Russian Science Foundation (project no. 18-73-10206). The work was supported by the Russian Foundation for Basic Research (projects nos. 17-03-00355, 18-03-00228, 18-33-00632) and the Program “5-100” of the Russian People’s Friendship University. Equipment of the Center for Collective Use of Physical Investigation Methods, Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, was used.
XRD studies of of the complex IIb were carried out with the support of the National Research Center Kurchatov Institute (Order 2683 of November 25, 2018).
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