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Electronic structure of four-coordinate C-3v nickel(II) scorpionate complexes: Investigation by high-frequency and -field electron paramagnetic resonance and electronic absorption spectroscopies

Desrochers, P. J.; Telser, J.; Zvyagin, S. A.; Ozarowski, A.; Krzystek, J.; Vicic, D. A.


A series of complexes of formula Tp*NiX, where Tp*(-)) hydrotris( 3,5-dimethylpyrazole) borate and X) Cl, Br, I, has been characterized by electronic absorption spectroscopy in the visible and near-infrared ( NIR) region and by high-frequency and -field electron paramagnetic resonance ( HFEPR) spectroscopy. The crystal structure of Tp*NiCl has been previously reported; that for Tp*NiBr is given here: space group) Pmc2(1), a) 13.209( 2) angstrom, b) 8.082( 2) angstrom, c) 17.639( 4) angstrom, alpha = beta = gamma = 90 degrees, Z = 4. Tp*NiX contains a four- coordinate nickel( II) ion ( 3d(8)) with approximate C-3v point group symmetry about the metal and a resulting S= 1 high-spin ground state. As a consequence of sizable zero-field splitting ( zfs), Tp*NiX complexes are "EPR silent" with use of conventional EPR; however, HFEPR allows observation of multiple transitions. Analysis of the resonance field versus the frequency dependence of these transitions allows extraction of ! the full set of spin Hamiltonian parameters. The axial zfs parameter for Tp*NiX displays pronounced halogen contributions down the series: D) +3.93( 2), -11.43( 3), -22.81( 1) cm(-1), for X = Cl, Br, I, respectively. The magnitude and change in sign of D observed for Tp*NiX reflects the increasing bromine and iodine spin - orbit contributions facilitated by strong covalent interactions with nickel( II). These spin Hamiltonian parameters are combined with estimates of 3d energy levels based on the visible-NIR spectra to yield ligand-field parameters for these complexes following the angular overlap model ( AOM). This description of electronic structure and bonding in a pseudotetrahedral nickel( II) complex can enhance the understanding of similar sites in metalloproteins, both native nickel enzymes and nickel-substituted zinc enzymes.

  • Inorganic Chemistry 45(2006), 8930-8941


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