(MU-NITRIDO)((TETRAPHENYLPORPHYRINATO)IRON) AND ITS FE-RU ANALOG - REDOX BEHAVIOR AND CHARACTERIZATION OF NEW FE(IV)-CONTAINING SPECIES - X-RAY CRYSTAL-STRUCTURE OF [(THF)(TPP)FE-N-FEPC(H2O)](I-5).2THF
(MU-NITRIDO)((TETRAPHENYLPORPHYRINATO)IRON) AND ITS FE-RU ANALOG - REDOX BEHAVIOR AND CHARACTERIZATION OF NEW FE(IV)-CONTAINING SPECIES - X-RAY CRYSTAL-STRUCTURE OF [(THF)(TPP)FE-N-FEPC(H2O)](I-5).2THF
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DOI：
10.1021/ic00114a010
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发表时间：
1995-05-10
影响因子：
4.6
通讯作者：
TRIGIANTE, G
中科院分区：
文献类型：
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作者：
ERCOLANI, C;JUBB, J;TRIGIANTE, G
本文报道了混合配体Fe-N-桥连的、形式上混合价态的Fe（III）-Fe（IV）物种（TPP）Fe-N-FePc和杂环类似物（TPP）Fe-N-RuPc的制备和表征，并研究了它们的氧化还原性质。这些物质与I-2的氧化在两种情况下都导致带单正电荷的Fe-Fe和Fe-Ru μ-氮化物二聚体，具有I-5（-）作为抗衡离子。通过与NaBH 4反应，这些盐样物质被还原为起始材料。配合物[（THF）（TPP）Fe-N-FePc（H2O）]（I-5）的结构。2 THF已通过X射线研究阐明。该配合物属于单斜晶系。单元格数据：分子式C88 H70 Fe 2 I5 N13 O 4，M = 2119.94，a = 27.13（1）埃，B = 12.032（5）埃，c = 25.596（41）埃，V = 8298（20）埃（3），Z = 4，空间群Cc。该结构表明，酞菁和四苯基卟啉环通过接近线性的三原子Fe-N-Fe部分（179度）保持在一起。分子内的每个Fe原子位于相应大环的平面中，六配位分别通过在PcFe和（TPP）Fe位点处的H2O和THF分子的外部轴向连接来实现。H2O分子与另外两个THF分子氢键结合。I-5（-）离子呈V形，单独存在于晶体中。从红外光谱、拉曼光谱、穆斯堡尔谱和电子顺磁共振谱以及磁化率数据中获得了关于本Fe-Fe和Fe-Ru物种的分子和电子结构的额外信息。
The mixed-ligand bimetallic N-bridged, formally mixed-valence Fe(III)-Fe(IV) species (TPP)Fe-N-FePc, previously reported, and the heterobimetallic analogue (TPP)Fe-N-RuPc have been prepared and characterized, and their redox properties have been examined. Oxidation of these species with I-2 leads in both cases to monopositively charged Fe-Fe and Fe-Ru mu-nitrido dimers, having I-5(-) as counterion. By reaction with NaBH4, these salt-like species are reduced to the starting materials. The structure of the complex [(THF)(TPP)Fe-N-FePc(H2O)](I-5) . 2THF has been elucidated by an X-ray study. The complex crystallizes in the monoclinic system. Unit cell data: formula C88H70Fe2I5N13O4, M = 2119.94, a = 27.13(1) Angstrom, b = 12.032(5) Angstrom, c = 25.596(41) Angstrom, V = 8298(20) Angstrom(3), Z = 4, space group Cc. The structure shows that the phthalocyanine and tetraphenylporphyrin rings are held together by the nearly linear triatomic Fe-N-Fe moiety (179 degrees). Each Fe atom within the molecule lies in the plane of the respective macrocycle, six-coordination being achieved by external axial ligation of H2O and THF molecules at the PcFe and (TPP)Fe sites, respectively. The H2O molecule is hydrogen-bonded to two additional THF molecules. The I-5(-) ion is V-shaped and lies separately in the crystal. Additional information on the molecular and electronic structure of the present Fe-Fe and Fe-Ru species has been obtained from IR, Raman, Mossbauer, and EPR spectra and also from magnetic susceptibility data.