Renner M W, Fajer J
Energy Sciences and Technology Department, Brookhaven National Laboratory, Upton, NY 11974-5000, USA.
J Biol Inorg Chem. 2001 Oct;6(8):823-30. doi: 10.1007/s007750100276.
The oxidative chemistry of nickel(II) porphyrins is reviewed. Whether electron abstraction occurs from the metal to yield Ni(III) or from the porphyrin to yield Ni(II) pi cation radicals is discussed in terms of the relative energy levels of the metal and porphyrin orbitals. The effects of axial ligands in further modulating this ordering as well as the orbital occupancy of Ni(III) are also reviewed. Structural considerations, based on existing stereochemical data for Ni(I), high spin Ni(II) and related Ni(III) tetraaza complexes, are used to predict the metrics of Ni(III) porphyrins for which no structural data are available.
本文综述了镍（II）卟啉的氧化化学。从金属失去电子生成Ni（III），还是从卟啉失去电子生成Ni（II）π阳离子自由基，这一问题将根据金属和卟啉轨道的相对能级进行讨论。文中还综述了轴向配体在进一步调节这种能级顺序以及Ni（III）轨道占据方面的作用。基于现有的Ni（I）、高自旋Ni（II）及相关Ni（III）四氮杂环配合物的立体化学数据进行结构考量，以此预测尚无结构数据的Ni（III）卟啉的参数。
