β-Nitro derivatives of iron corrolates.
β-Nitro derivatives of iron corrolates.
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DOI：
10.1021/ic3002459
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发表时间：
2012-03-19
影响因子：
4.6
通讯作者：
Paolesse R
中科院分区：
文献类型：
--
作者：
Nardis S;Stefanelli M;Mohite P;Pomarico G;Tortora L;Manowong M;Chen P;Kadish KM;Fronczek FR;McCandless GT;Smith KM;Paolesse R
发展了两种不同的方法，对不同的meso-三芳基可罗进行区域选择性硝化，得到相应的β-取代硝基可罗铁配合物。一个两步程序提供三个铁（III）亚硝酰基产品-未取代的咔咯，3-硝基咔咯和3，17-二硝基咔咯。相比之下，一锅法合成方法几乎完全驱动反应形成亚硝酰铁3，17-二硝基咔咯。与合成具有吸电子官能团的类似三芳基可咯相比，三芳基可咯的meso-芳基上的释放电子取代基诱导更高的产率和更长的反应时间，这些结果可以确信地归因于中间体铁可咯π-阳离子自由基的容易形成和稳定。三芳基可咯的内消旋芳基上的吸电子取代基似乎也使轴向亚硝酰基不稳定，在五氟苯基可咯衍生物的情况下，这导致直接形成二取代的铁μ-氧代二聚体络合物。研究了内消旋芳基取代基对硝化反应进程和产物的影响。此外，为了阐明影响这些不同的铁亚硝酰基配合物的氧化还原反应性的最重要的因素，所选化合物进行了检查，通过循环伏安法和薄层紫外可见或FTIR光谱电化学在二氯甲烷。
Two different methods for the regioselective nitration of different meso-triarylcorroles leading to the corresponding β-substituted nitrocorrole iron complexes have been developed. A two-step procedure affords three Fe(III) nitrosyl products - the unsubstituted corrole, the 3-nitrocorrole and the 3,17-dinitrocorrole. In contrast, a one-pot synthetic approach drives the reaction almost exclusively to formation of the iron nitrosyl 3,17-dinitrocorrole. Electron-releasing substituents on the meso-aryl groups of the triarylcorroles induce higher yields and longer reaction times than what is observed for the synthesis of similar triarylcorroles with electron-withdrawing functionalities, and these results can be confidently attributed to the facile formation and stabilization of an intermediate iron corrole π-cation radical. Electron-withdrawing substituents on the meso-aryl groups of triarylcorrole also seem to labilize the axial nitrosyl group which, in the case of the pentafluorophenylcorrole derivative, results in the direct formation of a disubstituted iron μ-oxo dimer complex. The influence of meso-aryl substituents on the progress and products of the nitration reaction was investigated. In addition, to elucidate the most important factors which influence the redox reactivity of these different iron nitrosyl complexes, selected compounds were examined by cyclic voltammetry and thin-layer UV-visible or FTIR spectroelectrochemistry in CH2Cl2.
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影响因子：
4.7
作者：
Kanamori, Akiyasu;Catrinescu, Maria-Magdalena;Levin, Leonard A.
通讯作者：
Levin, Leonard A.
影响因子：
4.3
作者：
Gatto, Emanuela;Malik, Muhammad A.;Filippini, Daniel
通讯作者：
Filippini, Daniel
影响因子：
6.1
作者：
Altomare, A;Burla, MC;Spagna, R
通讯作者：
Spagna, R
影响因子：
4.6
作者：
Mastroianni, Marco;Zhu, Weihua;Paolesse, Roberto
通讯作者：
Paolesse, Roberto
影响因子：
4.3
作者：
Barbe, Jean-Michel;Canard, Gabriel;Guilard, Roger
通讯作者：
Guilard, Roger