Different Ways To Distort a Tetracapped Tetrahedron on Route to Forming an E4M4 Cubane: The Case of [E4(Pd(PPh2Me)2)4][Ph2EX2]2 (E = Sb, X = Cl; E = Bi, X = Br)
| Autor: | Ilse Y. Guzman-Jimenez, Joseph L. Stark, ‡ and Jean-François Halet, Jean-Yves Saillard, Brian Harms, Régis Gautier, Kenton H. Whitmire |
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| Rok vydání: | 1999 |
| Předmět: |
Hypervalent molecule
chemistry.chemical_element General Chemistry Electronic structure Biochemistry Catalysis Metal Crystallography chemistry.chemical_compound Colloid and Surface Chemistry chemistry Bromide Cubane Computational chemistry visual_art Cluster (physics) visual_art.visual_art_medium Electron counting Palladium |
| Zdroj: | Journal of the American Chemical Society. 121:4409-4418 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja982902u |
| Popis: | Tetrakis(diphenylmethylphosphine)palladium reacts with diphenylantimony chloride or diphenylbismuth bromide to give [E4(PdL2)4][Ph2EX2]2 (L = PPh2Me, 1: E = Sb, X = Cl; 2: E = Bi, X = Br) which have been characterized spectroscopically and by single-crystal X-ray diffraction for [Sb4(PdL2)4][Ph2SbCl2]2·0.5THF and [Bi4(PdL2)4][Ph2BiBr2]2. These compounds are electron-rich based on electron counting formalisms. The additional cluster electrons can be rationalized by the ability of group 15 elements to show hypervalency, particularly those elements such as Sb and Bi which show more metal character. The electronic structure of the compounds and of related species has been examined by EHT and DFT calculations. Relationships to other cubane-derived structures are derived, and the stability of structurally related M4E4 hypothetical clusters is discussed. Compounds 1 and 2 decompose thermally to give Bi2Pd and SbPd. |
| Databáze: | OpenAIRE |
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