Kieber-Emmons Matthew T, Riordan Charles G
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.
Acc Chem Res. 2007 Jul;40(7):618-25. doi: 10.1021/ar700043n. Epub 2007 May 23.
The monovalent oxidation state of nickel has received a growing amount of attention in recent years, in part due to its suggested catalytic role in a number of metalloprotein-mediated transformations. In coordination chemistry, nickel(I) is suitable for reductive activation of dioxygen, provided ligands are used that stabilize this less common oxidation state against disproportionation reactions. Two distinct molecular systems have been explored, which have provided access to new nickel-dioxygen structure types, namely, monomeric side-on and end-on superoxo and trans-micro-1,2-peroxo-dinickel complexes. The geometric and electronic structures of the complexes have been established by advanced spectroscopic methods, including resonance Raman and X-ray absorption spectroscopies, and augmented by density functional theory analyses.
近年来，镍的一价氧化态受到了越来越多的关注，部分原因是它在许多金属蛋白介导的转化过程中被认为具有催化作用。在配位化学中，如果使用能稳定这种较不常见氧化态以防止歧化反应的配体，镍（I）适合于对双氧进行还原活化。人们已经探索了两种不同的分子体系，它们提供了获得新型镍-双氧结构类型的途径，即单体侧基配位和端基配位的超氧配合物以及反式-微-1,2-过氧-二镍配合物。这些配合物的几何结构和电子结构已通过先进的光谱方法确定，包括共振拉曼光谱和X射线吸收光谱，并通过密度泛函理论分析得到补充。
