Soma Shoko, Van Stappen Casey, Kiss Mercedesz, Szilagyi Robert K, Lehnert Nicolai, Fujisawa Kiyoshi
Department of Chemistry, Ibaraki University, Mito, Ibaraki, 310-8512, Japan.
Department of Chemistry and Department of Biophysics, University of Michigan, 930 N. University Avenue, Ann Arbor, MI, 48109, USA.
J Biol Inorg Chem. 2016 Sep;21(5-6):757-75. doi: 10.1007/s00775-016-1366-7. Epub 2016 Jun 27.
The linear nickel-nitrosyl complex [Ni(NO)(L3)] supported by a highly hindered tridentate nitrogen-based ligand, hydrotris(3-tertiary butyl-5-isopropyl-1-pyrazolyl)borate (denoted as L3), was prepared by the reaction of the potassium salt of the ligand with the nickel-nitrosyl precursor [Ni(NO)(Br)(PPh 3 ) 2 ]. The obtained nitrosyl complexes as well as the corresponding chlorido complexes [Ni(NO)(Cl)(PPh 3 ) 2 ] and [Ni(Cl)(L3)] were characterized by X-ray crystallography and different spectroscopic methods including IR/far-IR, UV-Vis, NMR, and multi-edge X-ray absorption spectroscopy at the Ni K-, Ni L-, Cl K-, and P K-edges. For comparative electronic structure analysis we also performed DFT calculations to further elucidate the electronic structure of [Ni(NO)(L3)]. These results provide the nickel oxidation state and the character of the Ni-NO bond. The complex [Ni(NO)(L3)] is best described as [Ni (II) (NO (-) )(L3)], and the spectroscopic results indicate that the phosphane complexes have a similar [Ni (II) (NO (-) )(X)(PPh 3 ) 2 ] ground state.
由高度位阻的三齿氮基配体氢三（3 - 叔丁基 - 5 - 异丙基 - 1 - 吡唑基）硼酸盐（表示为L3）支撑的线性镍 - 亚硝酰基配合物[Ni(NO)(L3)]，是通过该配体的钾盐与镍 - 亚硝酰基前体[Ni(NO)(Br)(PPh₃)₂]反应制备的。所得到的亚硝酰基配合物以及相应的氯配合物[Ni(NO)(Cl)(PPh₃)₂]和[Ni(Cl)(L3)]通过X射线晶体学和不同的光谱方法进行了表征，这些光谱方法包括在Ni K -、Ni L -、Cl K - 和P K - 边的红外/远红外、紫外 - 可见、核磁共振和多边缘X射线吸收光谱。为了进行比较电子结构分析，我们还进行了密度泛函理论（DFT）计算，以进一步阐明[Ni(NO)(L3)]的电子结构。这些结果提供了镍的氧化态和Ni - NO键的性质。配合物[Ni(NO)(L3)]最好描述为[Ni (II) (NO⁻)(L3)]，并且光谱结果表明膦配合物具有类似的[Ni (II) (NO⁻)(X)(PPh₃)₂]基态。
