T-Shaped Gold→Stiborane Complexes as Carbophilic Catalysts: Influence of the Peripheral Substituents
| Autor: | Srobona Sen, Iou-Sheng Ke, François P. Gabbaï |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Steric effects
010405 organic chemistry Stereochemistry Organic Chemistry Cationic polymerization 010402 general chemistry 01 natural sciences Medicinal chemistry 0104 chemical sciences Catalysis Inorganic Chemistry chemistry.chemical_compound chemistry Phenylacetylene Transition metal Hexafluorophosphate Hydroamination Physical and Theoretical Chemistry Benzamide |
| Zdroj: | Organometallics. 36:4224-4230 |
| ISSN: | 1520-6041 0276-7333 |
| Popis: | As part of our efforts toward the discovery of new late transition metal catalysts, we synthesized [(o-(Ph2P)C6H4)2(o-C6Cl4O2)SbPh)Au]+ (3+) and [(o-(iPr2P)C6H4)2(o-C6Cl4O2)SbPh)Au]+ (4+), two cationic bis(phosphino)gold stiborane complexes, which were isolated as their hexafluorophosphate salts and fully characterized. Structural and computational studies indicate that the cores of these two complexes are almost structurally and electronically identical. Despite these similarities, these two complexes exhibit different catalytic activities in the hydroamination of phenylacetylene using anilines or in the cyclization of N-(prop-2-yn-1-yl)benzamide. Indeed, whereas 3+ catalyzes both reactions, we found that 4+ is inactive. The data collected on these two complexes suggest that the origin of this contrasting behavior is steric, rather than electronic, with the relatively bulky iPr2P ancillary ligands blocking access to the reactive gold center. |
| Databáze: | OpenAIRE |
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