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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis and characterisation of low valent Mn-complexes as models for Mn-catalases
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Synthesis and characterisation of low valent Mn-complexes as models for Mn-catalases

机译:低价锰配合物的合成和表征作为锰催化的模型

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In this work we report the synthesis of two novel manganese complexes, [L1_3Mn~(II)_6](ClO_4)_6 (1·(ClO_4)_6) and [L2Mn~(II)_2(μ-OAc)(μ-Cl)](ClO_4)_2 (2·(ClO_4)_2), where L1~(2-) is the 2,2′-(1,3-phenylenebis(methylene))bis((2-(bis(pyridin-2-ylmethyl)amino) ethyl)azanediyl)diacetic acid anion and L2 is N1,N1′-(1,3- phenylenebis(methylene))bis(N2,N2′-bis(pyridin-2-ylmethyl)ethane-1, 2-diamine). The ligands Na_2L1 and L2 are built on the same backbone, L2 only contains nitrogen donors, while two carboxylate arms have been introduced in Na_2L1. The two complexes have been characterized by single-crystal X-ray diffraction, magnetic susceptibility, EPR spectroscopy, and electrochemistry. X-Ray crystallography revealed that 1 is a manganese(ii) hexamer and 2 is a manganese(ii) dimer featuring an unprecedented mono-μ-acetato, mono-μ-chlorido bridging motif. The ability of the complexes to catalyse H_2O_2 disproportionation, thereby acting as models for manganese catalases, has been investigated and compared to the activity of two other related manganese complexes. The introduction of carboxylate donors in the ligands, leading to increased denticity, resulted in a drop in H_2O_2 disproportionation activity.
机译:在这项工作中,我们报告了[L1_3Mn〜(II)_6](ClO_4)_6(1·(ClO_4)_6)和[L2Mn〜(II)_2(μ-OAc)(μ-Cl )](ClO_4)_2(2·(ClO_4)_2),其中L1〜(2-)是2,2'-(1,3-亚苯基双(亚甲基))bis((2-(双(吡啶基-2 -基甲基)氨基)乙基)氮杂二基)二乙酸阴离子和L2为N1,N1'-(1,3-亚苯基双(亚甲基))双(N2,N2'-双(吡啶-2-基甲基)乙烷-1,2 -二胺)。配体Na_2L1和L2建立在同一骨架上,L2仅包含氮供体,而Na_2L1中引入了两个羧酸根。两种配合物的特征在于单晶X射线衍射,磁化率,EPR光谱和电化学。 X射线晶体学分析显示1是锰(ii)六聚体,2是锰(ii)二聚体,具有前所未有的单-乙酰,单-氯桥联基序。已经研究了配合物催化H_2O_2歧化的能力,从而作为锰过氧化氢酶的模型,并将其与另外两种相关的锰配合物的活性进行了比较。在配体中引入羧酸盐供体,导致密度增加,导致H_2O_2歧化活性下降。

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