Theoretical investigation of paramagnetic group 13 diazabutadiene radicals: insights into the prediction and interpretation of EPR spectroscopy parameters

The electronic structures and the spin density distributions of the group 13 1,4-diaza(1,3)butadiene (DAB) radicals (R-DAB)2M]*, (R-DAB)MX2] and {(R-DAB)MX]2}** (M = Al, Ga, In; X = F, Cl, Br, I; R = H, Me, tBu, Ph) are studied using density functional theory at both non-relativistic and relativistic levels of theory. The calculations demonstrate that all systems share a qualitatively similar electronic structure and are primarily ligand centred pi-radicals. The calculated metal, nitrogen and hydrogen hyperfine couplings are found to be independent of the identity of the R-group and the halogen atom. They are, however, dependent on the geometry and oxidation state of the metal centre. Both observed trends contrast what has previously been deduced from the interpretation of experimental EPR and ENDOR spectra. Good agreement between the calculated and experimentally determined hyperfine coupling constants is found only for some of the studied systems. Instances where significant discrepancies between the calculated and experimental values exist can be attributed to the tendency of these systems toward complex solution behaviour, which results in differences between the solid state and solution structures of certain complexes. A careful re-evaluation of the experimental data as well as calculated reaction energies lends strong support to this hypothesis. However, further studies are needed before the identity of some of the studied radical species in solution can be unambiguously determined.