Huyett Jennifer E., Choudhury Suranjan B., Eichhorn David M., Bryngelson Peter A., Maroney Michael J., Hoffman Brian M.
Departments of Chemistry, Northwestern University, Evanston, Illinois 60208-3113, and University of Massachusetts, Amherst, Massachusetts 01003-4510.
Inorg Chem. 1998 Mar 23;37(6):1361-1367. doi: 10.1021/ic9703639.
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.
通过结合Q波段脉冲ENDOR（电子核双共振）和X波段ESEEM（电子激发回波包络调制）技术，我们已经确定了Ni(mnt)(2)中乙烯基（C1）、氰基（C2）碳原子以及氮原子的超精细张量，以及氮原子的四极张量。这些测量结果给出了C1 2p(z)()轨道中ρ(C1)约为0.03、ρ(C2) < 0.003、ρ(N)约为0.01的π电子自旋密度，使得总的来说，约0.15的自旋位于配体原子C和N上，而其余的自旋位于NiS(4)核心中，得到ρ(NiS(4)(-)) = 0.85。将这些结果与扩展休克尔和密度泛函（BLYP）分子轨道计算以及早期报道的Xalpha计算进行了比较。
