Issue 3, 2011

Dinitrogen complexation with main group radicals

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.

Graphical abstract: Dinitrogen complexation with main group radicals

Supplementary files

Article information

Article type
Edge Article
Submitted
22 Jun 2010
Accepted
09 Nov 2010
First published
25 Nov 2010

Chem. Sci., 2011,2, 473-479

Dinitrogen complexation with main group radicals

D. Kurzbach, A. Sharma, D. Sebastiani, K. W. Klinkhammer and D. Hinderberger, Chem. Sci., 2011, 2, 473 DOI: 10.1039/C0SC00345J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements