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 (Cl) and cyano (C2) carbons and N, of [Ni(mnt)2]-, along with the quadrupole tensor for nitrogen. These measurements give π electron spin densities of ρ(Cl) ∼ 0.03 in the Cl 2pz orbital, ρ(C2) < 0.003, ρ(N) ∼ 0.01, such that in total, ∼0.15 of the spin resides on the ligand atoms C and N, while the rest resides in the NiS4 core, giving ρ(NiS4-) = 0.85. These results are compared with extended Hückel and density functional (BLYP) MO calculations, as well as with Xα calculations reported earlier.
|Original language||English (US)|
|Number of pages||7|
|State||Published - Dec 1 1998|
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry