Acid/Base-Controlled AuI/Au0 Reductive Transformations of the Monogold [(μ14-Au)Pd22(CO)20(PEt3)8]+ Monocation into Three Different Neutral Digold Nanoclusters: Au2Pd21(CO)20(PEt3)10, Au2Pd28(CO)26(PEt3)10, and New Five-Layer Hexagonal Close-Packed (μ12-Au)2Pd42(CO)30(PEt3)12 with a Trigonal-Bipyramidal AuPd3Au Kernel
| Autor: | Lawrence F. Dahl, Evgueni G. Mednikov |
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| Rok vydání: | 2014 |
| Předmět: |
chemistry.chemical_classification
Chemistry Stereochemistry Close-packing of equal spheres Nanoclusters Inorganic Chemistry Trigonal bipyramidal molecular geometry Crystallography chemistry.chemical_compound Yield (chemistry) Molecule Physical and Theoretical Chemistry Counterion Bimetallic strip Carbon monoxide |
| Zdroj: | Inorganic Chemistry. 54:1145-1151 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic502470m |
| Popis: | The monogold [(μ14-Au)Pd22(CO)20(PEt3)8]+ nanocation (2, with a [(CF3CO2)2H]− counterion) is shown to be a versatile precursor for the generation of three different neutral Au–Pd nanoclusters with double gold content in their distinctly dissimilar bimetallic architectures. These carbon monoxide (CO)-induced conversions are based on the reduction of AuI to Au0 that is controlled by the reaction medium. Under basic and acidic conditions, the known Au2Pd21(CO)20(PEt3)10 (3; >90% yield) and Au2Pd28(CO)26(PEt3)10 (4; ∼40% yield), respectively, were obtained, whereas neutral conditions gave rise to the new (μ12-Au)2Pd42(CO)30(PEt3)12 (1; ∼10–20% yield; all yields based on gold). The molecular structure of 1, established from a 100 K CCD X-ray diffraction study, consists of a five-layer hexoganol close-packed (hcp) Au2Pd42 framework of pseudo-D3h symmetry (crystallographic D3 site symmetry) of the Pd6/AuPd9/Pd12/AuPd9/Pd6 layer sequence, with the Au atoms centering two identical hcp (μ12-Au)Pd12 face-fused anti-... |
| Databáze: | OpenAIRE |
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