Reversible Gas–Solid Ammonia N–H Bond Activation Mediated by an Organopalladium Complex
| Autor: | Marina Juribašić Kulcsar, Krunoslav Užarević, Ana Budimir, Andrea Monas, Stipe Lukin, Manda Ćurić, Janez Plavec, Ivan Halasz, Franziska Emmerling |
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| Rok vydání: | 2017 |
| Předmět: |
010405 organic chemistry
Hydrogen bond Gas solid 010402 general chemistry Photochemistry 01 natural sciences 0104 chemical sciences Inorganic Chemistry symbols.namesake chemistry.chemical_compound Azobenzene chemistry Mechanochemistry Organopalladium N-H activation gas-solid reaction dipalladated complex spectroscopy DFT calculations symbols Density functional theory Physical and Theoretical Chemistry Raman spectroscopy Ammonia n |
| Zdroj: | Inorganic Chemistry. 56:5342-5351 |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | N−H bond activation of gaseous ammonia is achieved at room temperature in a reversible solvent-free reaction using a solid dicyclopalladated azobenzene complex. Monitoring of the gas−solid reaction in real-time by in situ solid-state Raman spectroscopy enabled a detailed insight into the stepwise activation pathway proceeding to the final amido complex via a stable diammine intermediate. Gas−solid synthesis allowed for isolation and subsequent structural characterization of the intermediate and the final amido product, which presents the first dipalladated complex with the PdII−(μ-NH2)−PdII bridge. Gas−solid reaction is readily followed via color changes associated with conformational switching of the palladated azobenzene backbone. The reaction proceeds analogously in solution and was characterized by UV−vis and NMR spectroscopies showing the same stepwise route to the amido complex. Combining the experimental data with density functional theory calculations we propose a stepwise mechanism of this heterolytic N−H bond activation assisted by exogenous ammonia. |
| Databáze: | OpenAIRE |
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