Isolation and Structural Characterization of a Mackay 55-Metal-Atom Two-Shell Icosahedron of Pseudo-Ih Symmetry, Pd55L12(μ3-CO)20 (L = PR3, R = Isopropyl): Comparative Analysis with Interior Two-Shell Icosahedral Geometries in Capped Three-Shell Pd145, Pt-Centered Four-Shell Pd–Pt M165, and Four-Shell Au133 Nanoclusters
| Autor: | Evgueni G. Mednikov, Jeremiah D. Erickson, Sergei A. Ivanov, Lawrence F. Dahl |
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| Rok vydání: | 2016 |
| Předmět: |
010405 organic chemistry
Icosahedral symmetry Shell (structure) Charge (physics) General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Catalysis 0104 chemical sciences Nanoclusters Metal chemistry.chemical_compound Crystallography Colloid and Surface Chemistry chemistry Computational chemistry visual_art Atom visual_art.visual_art_medium Isopropyl Phosphine |
| Zdroj: | Journal of the American Chemical Society. 138:1502-1505 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.5b13076 |
| Popis: | We present the first successful isolation and crystallographic characterization of a Mackay 55-metal-atom two-shell icosahedron, Pd55L12(μ3-CO)20 (L = PPri3) (1). Its two-shell icosahedron of pseudo-Ih symmetry (without isopropyl substituents) enables a structural/bonding comparison with interior 55-metal-atom two-shell icosahedral geometries observed within the multi-shell capped 145-metal-atom three-shell Pd145(CO)72(PEt3)30 and 165-metal-atom four-shell Pt-centered (μ12-Pt)Pd164-xPtx(CO)72(PPh3)20 (x ≈ 7) nanoclusters, and within the recently reported four-shell Au133(SC6H4-p-But)52 nanocluster. DFT calculations carried out on a Pd55(CO)20(PH3)12 model analogue, with triisopropyl phosphine substituents replaced by H atoms, revealed a positive +0.84 e charge for the entire Pd55 core, with a highly positive second-shell Pd42 surface of +1.93 e. |
| Databáze: | OpenAIRE |
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