Ligand hyperfine and exchange interactions in a low-spin d⁷ system

Abstract

The single crystal EPR results of [NiBr₂(diars)₂]Br, a low spin Ni(III) complex,magnetically diluted in [Co(NO)Br(diars)₂]Br show a very large bromine hyperfine coupling. The experimental g, ligand hyperfine splitting due to arsenic and bromine and spin densities are compared with other analogous diphos and diars complexes. The unpaired electron is essentially in the d_z2 orbital and there is extensive delocalization over alla the ligand nuclei due to extended 4s and 4p radial wave functions. On the other hand the pure crystal of [NiBr₂(diars)₂]Br shows single exchange averaged EPR line. Linewidth analysis using the existing theories of exchange gives values of roughly 800G and 380G for respectively isotropic and intersite exchange interactions in this system.