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| Content Provider | Royal Society of Chemistry (RSC) |
|---|---|
| Author | Klinkhammer, Karl W. Sebastiani, Daniel Kurzbach, Dennis Hinderberger, Dariush Sharma, Ajay |
| Copyright Year | 2011 |
| Abstract | In this report we present data from hyperfine sublevel correlation spectroscopy (HYSCORE), an electron paramagnetic resonance (EPR) spectroscopic technique, that reveals weak but distinct interactions between several main group element radicals and physically dissolved dinitrogen in solution. These interactions are the basis for a well-defined coordination of N2 to the paramagnetic centers. The complexes formed are primarily of the van der Waals-type but also feature a non-negligible orbital overlap between dinitrogen and the radicals' SOMO. Our spectroscopic findings are strongly supported by experiments with isotope-labeled 15N2, spectral simulations and quantum chemical and density functional theory (DFT) calculations. Formation of such complexes is unexpected when considering the small polarizability of dinitrogen but steric effects like formation of a binding “pocket” may facilitate their formation. The sensitivity, selectivity, and resolution of HYSCORE with respect to the detection of weak hyperfine couplings is needed to identify such complexes that are probably the result of a subtle interplay of induced van der Waals forces between N2, the solvent and the dissolved radicals. |
| Starting Page | 473 |
| Ending Page | 479 |
| Page Count | 7 |
| File Format | HTM / HTML PDF |
| ISSN | 20416520 |
| Volume Number | 2 |
| Issue Number | 3 |
| Journal | Chemical Science |
| DOI | 10.1039/c0sc00345j |
| Language | English |
| Publisher | Royal Society of Chemistry |
| Access Restriction | Open |
| Subject Keyword | Polarizability EPR Paramagnetism Steric effects Nitrogen Van der Waals force Hyperfine structure Two-dimensional nuclear magnetic resonance spectroscopy Quantum mechanics SOMO Interplay Entertainment Density functional theory Electron paramagnetic resonance Main-group element Solvent |
| Content Type | Text |
| Resource Type | Article |
| Subject | Chemistry |
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