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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Preparation and characterization of mu-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation
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Preparation and characterization of mu-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation

机译：具有吸电子取代基的mu-nitrido二铁酞菁的制备与表征：催化芳族氧化的应用

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摘要

mu-Nitrido-bis [tetra-(hexyl-sulfonyl)phthalocyaninatoiron] (3a) and mu-nitrido-bis [tetra-(tert-butylsulfonyl)phthalocyaninatoiron] (3b) complexes have been prepared and fully characterized by electrospray ionization mass spectrometry, UV-Vis, FTIR, EPR, Mossbauer techniques as well as by X-ray photoelectron and Fe K-edge X-ray absorption spectroscopies. Small changes at the periphery of the phthalocyanine ligand introduce a difference in the iron oxidation state. While 3b with tert-butyl substituents is a neutral complex with a mixed-valence Fe-3.5-N-Fe-3.5 structural unit, 3a having n-hexyl substituents is an oxidized cationic Fe-IV-N-Fe-IV complex. The structural parameters of N-bridged diiron phthalocyanine with a Fe-3.5-N-Fe-3.5 unit were determined for the first time. Iron atoms in 3b are displaced out of plane by 0.24 angstrom and the Fe-N bond distance of the linear Fe-N-Fe fragment is equal to 1.67 angstrom. Both complexes selectively catalyze benzylic oxidation of alkyl aromatic compounds by (BuOOH)-Bu-t. Toluene was oxidized to benzoic acid with 80% selectivity, and the total turnover number was as high as 197. p-Toluic acid was the principal product of p-xylene oxidation. In this case the turnover number achieved 587 substrate molecules per molecule of catalyst. The described catalytic system is complementary to the recently reported system based on mu-nitrido diiron tetrabutylphthalocyanine-H2O2 which effectively oxidizes the benzene ring.
机译：制备了μ-Nitrido-双[四-（己基-磺酰基）邻苯二甲酸酯基萘基铁]（3a）和μ-Ni-N-基-双[[4-（叔丁基磺酰基）邻苯二甲酸酯基萘基铁]（3b）配合物，并通过电喷雾电离质谱法对其进行了全面表征， UV-Vis，FTIR，EPR，Mossbauer技术以及通过X射线光电子和Fe K边缘X射线吸收光谱仪。酞菁配体外围的微小变化会引起铁氧化态的差异。具有叔丁基取代基的3b是具有混合价Fe-3.5-N-Fe-3.5结构单元的中性配合物，而具有正己基取代基的3a是氧化的阳离子Fe-IV-N-Fe-IV配合物。首次确定了具有Fe-3.5-N-Fe-3.5单元的N桥联二铁酞菁的结构参数。 3b中的铁原子平面外移位0.24埃，线性Fe-N-Fe片段的Fe-N键距离等于1.67埃。两种络合物通过（BuOOH）-Bu-t选择性地催化烷基芳族化合物的苄基氧化。甲苯以80％的选择性被氧化为苯甲酸，总周转数高达197。对甲苯甲酸是对二甲苯氧化的主要产物。在这种情况下，周转数达到每分子催化剂587个底物分子。所描述的催化体系是对最近报道的基于mu-nitrido二铁四丁基酞菁-H2O2的体系的补充，该体系有效氧化苯环。

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