Variations in the copper(I)-copper(I) distances in multinuclear clusters with identical coordination geometries. Short metal-metal contacts induced by oligomerization
| Autor: | Ashoka G. Samuelson, Santosh P. Abraham, Jayaraman Chandrasekhar |
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| Rok vydání: | 1993 |
| Předmět: | |
| Zdroj: | Inorganic Chemistry. 32:6107-6111 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic00078a032 |
| Popis: | Factors contributing to the variations in the Cu(I)-Cu(I) distances in two clusters with identical ligand and coordination geometries have been analyzed. While the hexamer, 4, exhibits metal-metal distances in the range 2.81-3.25 Angstrom, shorter contacts are found in the corresponding tetramer, 3 (2.60-2.77 Angstrom). EHT calculations reveal relatively little attractive interactions in the corresponding Cu-4(4+) and Cu-6(6+) cores. Introduction of the ligands lowers the reduced overlap populations between the metals further. MNDO calculations with model electrophiles have been carried out to determine the bite angle requirements of the ligands. These are satisfactorily met in the structures of both 3 and 4. The key geometric feature distinguishing 3 and 4 is the Cu-S-Cu angle involving the bridging S- unit. In 4, the corresponding angles are about 90 degrees, while the values in 3 are smaller (70-73 degrees). Wider angles are computed to be energetically favored and are characterized by an open three-center bond and a long Cu-Cu distance. The bridging angles are suggested to be primarily constrained by the mode of oligomerization. Implications of these results for the stability and reactivity of these clusters and for short metal-metal distances in d(10) systems in general are discussed. |
| Databáze: | OpenAIRE |
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