Stabilization of 3d Transition Metal Hydrido Complexes in SrH2Mg2[Co(I)H5], BaH2Mg5[Co(-I)H4]2, and RbH2Mg5[Co(-I)H4 Ni(0)H4] via Easily Polarizable Hydride Ligands.
Stabilization of 3d Transition Metal Hydrido Complexes in SrH2Mg2[Co(I)H5], BaH2Mg5[Co(-I)H4]2, and RbH2Mg5[Co(-I)H4 Ni(0)H4] via Easily Polarizable Hydride Ligands.
复制标题
通过易于极化的氢化物配体稳定 SrH2Mg2[Co(I)H5]、BaH2Mg5[Co(-I)H4]2 和 RbH2Mg5[Co(-I)H4 Ni(0)H4] 中的 3d 过渡金属氢化物配合物。
DOI：
10.1021/acs.inorgchem.6b00074
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发表时间：
2016
影响因子：
4.6
通讯作者：
Fahlquist H
中科院分区：
文献类型：
--
作者：
Fahlquist H
利用中子衍射、非弹性中子散射和第一性原理计算的综合研究描述了钴在BaH2Mg5[Co(−I)H4]2和结构相关的RbH2Mg5[Co(−I)H4Ni(0)H4]中略微扭曲的四面体Co(−I)H4配合物中具有非常低的（−I）形式氧化态。这表明，通过可极化氢化物离子对固态氢化物中的反离子的电子“回供”效应，可以与更传统的“回键”相比，能够将氧化态降低到- I。用相应的二元碱土氢化物和碱土氢化物对过渡金属粉末进行热烧结制备氢化物。在类似合成的SrH2Mg2[Co(I)H5]中，钴的形态为+ I价，对反离子框架的差异表现出高度敏感性，这也会影响电性能。
A combined study using neutron diffraction, inelastic neutron scattering, and first-principles calculations describe cobalt with a very low formal oxidation state of (−I) in a slightly distorted tetrahedral Co(−I)H4-complex in BaH2Mg5[Co(−I)H4]2and in the structurally related RbH2Mg5[Co(−I)H4Ni(0)H4]. This indicates that the electron “back donating” effect via the polarizable hydride ions to the counterions in the solid state hydrides, can be compared to more conventional “back bonding” able to reduce the oxidation state down to −I. The hydrides were synthesized by hot sintering of transition metal powders with corresponding binary alkali- and alkaline earth hydrides. In the similarly synthesized SrH2Mg2[Co(I)H5], cobalt is formally + I-valent, showing a high sensitivity to differences in the counterion framework, which can also influence electrical properties.