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首页> 外文期刊>Chemistry: A European journal >Homoleptic Organoderivatives of High-Valent Nickel(III)
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Homoleptic Organoderivatives of High-Valent Nickel(III)

机译：高价镍（III）的同质有机衍生物

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摘要

Homoleptic perhalophenylderivatives of divalent nickel com-plexes with the general formula[NBu_4]_2[Ni~(II)(C_6X_5)_4] [X =F (1), Cl 2)]have been prepared by low-tempera-ture treatment of the halo-complexprecursor [NBu_4]_2[NiBr_4] with the cor-responding organolithium reagentLiC_6X_5. Compounds 1 and 2 are elec-trochemically related by reversibleone-electron exchange processes withthe corresponding organometallate(III)compounds [NBu_4][Ni~(III)(C_6X_5)_4] [X = F(3), Cl (4)]. The potentials of the [Ni~(III)-(C_6X_5)_4]~-/[Ni~(II)(C_6X_5)_4]~(2-)couples are +0.07 and —0.11 V for X =F or Cl, re-spectively. Compounds 3 and 4 have also been prepared and isolated ingood yield by chemical oxidation of 1or 2 with bromine or the amminiumsalt [N(C_6H_4Br-4)_3][SbCl_6]. The [Ni~(III)-(C_6X_5)_4]~-species haveSP-4structuresin the salts 3 and 4, as established bysingle-crystal X-ray diffraction meth-ods. The [Ni~(II)(C_6F_5)_4]~(2-)ion in theparent compound 1 has also beenfound to exhibit a rather similar SP-4structure. According to their SP-4 ge-ometry, the Ni~(III) compounds (d7)behave as S = 1/2 systems both at micro-scopic (EPR) and macroscopic levels(ac and dc magnetization measure-ments). The spin Hamiltonian parame-ters obtained from the analysis of themagnetic behavior of 3 and 4 withinthe framework of ligand field theoryshow that the unpaired electron is cen-tered mainly on the metal atom, with> 97 % estimated d_z~2contribution.Thermal decomposition of 3 and 4 pro-ceeds with formation of the corre-sponding C_6X_5—C_5coupling com-pounds.
机译：通式[NBu_4] _2 [Ni〜（II）（C_6X_5）_4] [X = F（1），Cl 2）的二价镍络合物的全卤代苯基衍生物已经通过低温处理卤代络合物前体[NBu_4] _2 [NiBr_4]和相应的有机锂试剂LiC_6X_5。化合物1和2通过可逆的电子交换过程与相应的有机金属盐（III）化合物[NBu_4] [Ni〜（III）（C_6X_5）_4] [X = F（3），Cl（4）]电化学相关。 [Ni〜（III）-（C_6X_5）_4]〜// [Ni〜（II）（C_6X_5）_4]〜（2-）的电势在X = F或Cl时为+0.07和-0.11 V，分别。还已经通过用溴或铵盐[N（C_6H_4Br-4）_3] [SbCl_6]对1或2进行化学氧化来制备和分离化合物3和4，收率很高。 [Ni〜（III）-（C_6X_5）_4]〜在盐3和4中具有SP-4结构，这是通过单晶X射线衍射方法确定的。还发现母体化合物1中的[Ni〜（II）（C_6F_5）_4]〜（2-）离子表现出相当相似的SP-4结构。根据其SP-4几何形状，在微观（EPR）和宏观水平（交流和直流磁化强度测量）下，Ni〜（III）化合物（d7）的S = 1/2系统。通过在配体场论框架内对3和4的磁性行为进行分析获得的自旋哈密顿量参数表明，未配对电子主要集中在金属原子上，估计d_z〜2贡献大于97％.3的热分解和4个步骤，形成了对应的C_6X_5—C_5耦合化合物。

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