Pulsed ENDOR and ESEEM Study of [Bis(maleonitriledithiolato)nickel]-: An Investigation into the Ligand Electronic Structure Academic Article uri icon

abstract

  • By a combination of Q-band pulsed ENDOR (electron nuclear double resonance) and X-band ESEEM (electron stimulated echo envelope modulation) techniques, we have determined the hyperfine tensors for ethylene (C1) and cyano (C2) carbons and N, of [Ni(mnt)(2)](-), along with the quadrupole tensor for nitrogen. These measurements give pi electron spin densities of rho(C1) approximately 0.03 in the C1 2p(z)() orbital, rho(C2) < 0.003, rho(N) approximately 0.01, such that in total, approximately 0.15 of the spin resides on the ligand atoms C and N, while the rest resides in the NiS(4) core, giving rho(NiS(4)(-)) = 0.85. These results are compared with extended Hückel and density functional (BLYP) MO calculations, as well as with Xalpha calculations reported earlier.

author list (cited authors)

  • Huyett, J. E., Choudhury, S. B., Eichhorn, D. M., Bryngelson, P. A., Maroney, M. J., & Hoffman, B. M.

publication date

  • January 1, 1998 11:11 AM