The Properties of Hydrotris(3‐mesitylpyrazol‐1‐yl) Borate Iron(II) Complexes with Aryl Carboxylate Co‐ligands – Stabilization of an Iron(III) Alkylperoxide,Zeitschrift für anorganische und allgemeine Chemie

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The Properties of Hydrotris(3‐mesitylpyrazol‐1‐yl) Borate Iron(II) Complexes with Aryl Carboxylate Co‐ligands – Stabilization of an Iron(III) Alkylperoxide
Zeitschrift für anorganische und allgemeine Chemie ( IF 1.1 ) Pub Date : 2020-12-23 , DOI: 10.1002/zaac.202000437
Lars Müller ₁ , Kirill Baturin ₁ , Santina Hoof ₁ , Caroline Lau ₁ , Christian Herwig ₁ , Christian Limberg ₁

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Through the reaction of [Tp^MesFeCl] with different benzoic acids, namely salicylic acid (HOBz^o−OH), m‐chloro benzoic acid (HOBz^m−Cl), p‐dimethylamino benzoic acid (OBz^p−N(Me)2) and benzoic acid itself, in the presence of triethylamine corresponding complexes [Tp^MesFeOBz^R] with varying residues R could be isolated and fully characterized (including paramagnetic NMR spectroscopy, elemental analysis, IR, cyclic voltammetry). From acetonitrile solutions they crystallized as acetonitrile adducts [Tp^MesFe(NCMe)OBz^R], which indicates, that a coordination and activation of an exogeneous substrate is principally possible. While no reactivity towards O₂ could be observed, in contact with ^tBuOOH all complexes were found to form iron(III) tert‐butylperoxide complexes [Tp^MesFe(OBz^R)(OO^tBu)], as evidenced by UV‐vis, EPR and Raman spectroscopy. Through UV‐vis studies it was shown, that both the formation rate and the stability of [Tp^MesFe(OBz^R)(OO^tBu)] are influenced by the basicity of the benzoate co‐ligands, which is determined by the substituents. An extraordinarily high stability was observed for the salicylate representative, which, however, cannot be explained on basis of such electronic effects; other potential stabilizing factors that may play an important role are discussed.

中文翻译：

具有芳基羧酸盐共配体的氢化三（3-间苯并吡唑-1-基）硼酸铁（II）配合物的性质-烷基过氧化铁（III）的稳定化

通过[TP的反应^的Mes的FeCl]用不同的苯甲酸，即水杨酸（HOBz ^{Ò -OH}），米-氯苯甲酸（HOBz^米-Cl），p -二甲基氨基苯甲酸（OBZ ^{p -N（Me）的2}）和苯甲酸本身，在三乙胺存在下，具有不同残基R的相应配合物[Tp ^Mes FeOBz ^R ]可以被分离并充分表征（包括顺磁NMR光谱，元素分析，IR，循环伏安法）。它们从乙腈溶液中结晶为乙腈加合物[Tp ^Mes Fe（NCMe）OBz ^R]，这表明外源底物的配位和活化原则上是可能的。虽然未观察到对O _2的反应性，但发现与^t BuOOH接触时，所有络合物都形成了叔丁基过氧化铁（III）铁络合物[Tp ^Mes Fe（OBz ^R）（OO ^t Bu）]，通过UV-vis证明了这一点。，EPR和拉曼光谱。通过UV-vis研究表明，[Tp ^Mes Fe（OBz ^R）（OO ^tBu）]受苯甲酸酯共配体碱性的影响，该碱性由取代基决定。对于水杨酸盐代表，观察到非常高的稳定性，但是，不能基于这种电子效应来解释；讨论了可能发挥重要作用的其他潜在稳定因素。

更新日期：2021-02-26

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