Synthesis, Electronic Properties and Reactivity of [B 12 X 11 (NO 2 )] 2− (X=F–I) Dianions
| Autor: | Knut R. Asmis, Carsten Jenne, Björn B. Beele, Marc C. Nierstenhöfer, Harald Knorke, Ziyan Warneke, Xue-Bin Wang, Jonas Warneke, Qinqin Yuan, Sebastian Kawa |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
010405 organic chemistry
Chemistry Organic Chemistry Substituent Infrared spectroscopy General Chemistry 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences Homolysis Ion symbols.namesake chemistry.chemical_compound Crystallography X-ray photoelectron spectroscopy symbols Reactivity (chemistry) Cyclic voltammetry Raman spectroscopy |
| Zdroj: | Chemistry – A European Journal. 26:14594-14601 |
| ISSN: | 1521-3765 0947-6539 |
| Popis: | Nitro-functionalized undecahalogenated closo-dodecaborates [B12 X11 (NO2 )]2- were synthesized in high purities and characterized by NMR, IR, and Raman spectroscopy, single crystal X-diffraction, mass spectrometry, and gas-phase ion vibrational spectroscopy. The NO2 substituent leads to an enhanced electronic and electrochemical stability compared to the parent perhalogenated [B12 X12 ]2- (X=F-I) dianions evidenced by photoelectron spectroscopy, cyclic voltammetry, and quantum-chemical calculations. The stabilizing effect decreases from X=F to X=I. Thermogravimetric measurements of the salts indicate the loss of the nitric oxide radical (NO. ). The homolytic NO. elimination from the dianion under very soft collisional excitation in gas-phase ion experiments results in the formation of the radical [B12 X11 O]2-. . Theoretical investigations suggest that the loss of NO. proceeds via the rearrangement product [B12 X11 (ONO)]2- . The O-bonded nitrosooxy structure is thermodynamically more stable than the N-bonded nitro structure and its formation by radical recombination of [B12 X11 O]2-. and NO. is demonstrated. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
| Nepřihlášeným uživatelům se plný text nezobrazuje | K zobrazení výsledku je třeba se přihlásit. |