Synthesis and characterization of a modified "picket fence" porphyrin complex - stronger π bonding interactions between Fe(II) and axial ligands
Synthesis and characterization of a modified "picket fence" porphyrin complex - stronger π bonding interactions between Fe(II) and axial ligands
复制标题
改性“栅栏”卟啉配合物的合成和表征 - Fe(II) 和轴向配体之间更强的 pi 键相互作用
DOI：
10.1039/c5dt00941c
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发表时间：
2015-01-01
影响因子：
4
通讯作者：
Li, Jianfeng
中科院分区：
文献类型：
--
作者：
He, Baiyin;Schulz, Charles E.;Li, Jianfeng
合成了一种新型的“尖桩栅栏”卟啉，并研究了它的双(咪唑)-铁(II)衍生物[Fe(MbenTpivPP)(1-MeIm)(2)]。X-射线结构测定表明，[Fe(MbenTpivPP)(1-MeIm)2]具有近平面、相对垂直的配体取向和一个异常大的绝对配体取向(Phi)的结构特征。这些特征的结合导致了一种不同于以前报道的类似物的新类型的物种。进一步的结构分析表明，相互配体取向(Theta)与Fe-N-Im键轴向距离之间存在很强的相关性，这是首次详细描述的。穆斯堡尔谱表征表明，在100K时，低自旋导数的四极分裂为0.99 mm S(-1)。
A new, modified "picket fence" porphyrin is synthesized and its bis(imidazole)-ligated iron(II) derivative [Fe(MbenTpivPP)(1-MeIm)(2)] is investigated. X-ray structure determinations demonstrate that [Fe(MbenTpivPP)(1-MeIm) 2] has structural features of a near planar porphyrin plane, a relative perpendicular ligand orientation, and one unusually large absolute ligand orientation (phi). The combination of these features leads to a new type of species that is different from previously reported analogues. Further structural examination reveals a strong correlation between the mutual ligand orientations (theta) and the axial Fe-N-Im bond distances, which is detailed for the first time. Mossbauer spectroscopic characterization shows that the low spin derivative has a quadrupole splitting of 0.99 mm s(-1) at 100 K.