6533b855fe1ef96bd12b11be
RESEARCH PRODUCT
Dinitrogen complexation with main group radicals
Dennis KurzbachDariush HinderbergerKarl W. KlinkhammerAjay SharmaDaniel Sebastianisubject
Steric effectsChemistryGeneral ChemistryOrbital overlapPhotochemistrylaw.inventionsymbols.namesakeMain group elementComputational chemistryPolarizabilitylawsymbolsDensity functional theoryPhysics::Chemical Physicsvan der Waals forceElectron paramagnetic resonanceHyperfine structuredescription
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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2011-01-01 | Chem. Sci. |