Electronic Control of the 'Bailar Twist' in Formally d0-d2 Molybdenum Tris(dithiolene) Complexes: A Sulfur K-edge X-ray Absorption Spectroscopy and Density Functional Theory Study
| Autor: | Keith O. Hodgson, Adam L. Tenderholt, Robert K. Szilagyi, Britt Hedman, Edward I. Solomon, Richard H. Holm |
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| Rok vydání: | 2008 |
| Předmět: | |
| Zdroj: | Inorganic Chemistry. 47:6382-6392 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic800494h |
| Popis: | Sulfur K-edge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations have been used to determine the electronic structures of a series of Mo tris(dithiolene) complexes, [Mo(mdt)3]z (where mdt = 1,2-dimethylethene-1,2-dithiolate(2-) and z = 2−, 1−, 0), with near trigonal-prismatic geometries (D3h symmetry). These results show that the formally MoIV, MoV, and MoVI complexes actually have a (dz2)2 configuration, that is, remain effectively MoIV despite oxidation. Comparisons with the XAS data of another set of Mo tris(dithiolene) complexes, [Mo(tbbdt)3]z (where tbbdt = 3,5-ditert-butylbenzene-1,2-dithiolate(2-) and z = 1−, 0), show that both neutral complexes, [Mo(mdt)3] and [Mo(tbbdt)3], have similar electronic structures while the monoanions do not. Calculations reveal that the “Bailar twist” present in the crystal structure of [Mo(tbbdt)3]1− (D3 symmetry) but not [Mo(mdt)3]1− (D3h symmetry) is controlled by electronic factors which arise from bonding differences between the m... |
| Databáze: | OpenAIRE |
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