Metal-Templated, Tight Loop Conformation of a Cys-X-Cys Biomimetic Assembles a Dimanganese Complex.,Angewandte Chemie International Edition

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Metal-Templated, Tight Loop Conformation of a Cys-X-Cys Biomimetic Assembles a Dimanganese Complex.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-01-21 , DOI: 10.1002/anie.201913259
Trung Le ₁ , Hao Nguyen ₁ , Lisa M Perez ₁ , Donald J Darensbourg ₁ , Marcetta Y Darensbourg ₁

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With the goal of generating anionic analogues to MN2 S2 ⋅Mn(CO)3 Br we introduced metallodithiolate ligands, MN2 S2 2- prepared from the Cys-X-Cys biomimetic, ema4- ligand (ema=N,N'-ethylenebis(mercaptoacetamide); M=NiII , [VIV ≡O]2+ and FeIII ) to Mn(CO)5 Br. An unexpected, remarkably stable dimanganese product, (H2 N2 (CH2 C=O(μ-S))2 )[Mn(CO)3 ]2 resulted from loss of M originally residing in the N2 S2 4- pocket, replaced by protonation at the amido nitrogens, generating H2 ema2- . Accordingly, the ema ligand has switched its coordination mode from an N2 S2 4- cavity holding a single metal, to a binucleating H2 ema2- with bridging sulfurs and carboxamide oxygens within Mn-μ-S-CH2 -C-O, 5-membered rings. In situ metal-templating by zinc ions gives quantitative yields of the Mn2 product. By computational studies we compared the conformations of "linear" ema4- to ema4- frozen in the "tight-loop" around single metals, and to the "looser" fold possible for H2 ema2- that is the optimal arrangement for binucleation. XRD molecular structures show extensive H-bonding at the amido-nitrogen protons in the solid state.

中文翻译：

Cys-X-Cys仿生金属的金属模板的紧环构型组装了二锰配合物。

为了产生与MN2 S2⋅Mn（CO）3 Br相似的阴离子类似物，我们引入了金属二硫代金属盐配体，即由Cys-X-Cys仿生物ema4-配体（ema = N，N'-亚乙基双（巯基乙酰胺）制备的MN2 S2 2- ）; M = NiII，[VIV≡O] 2+和FeIII）生成Mn（CO）5 Br。出乎意料的，非常稳定的二锰产物（H2 N2（CH2 C = O（μ-S））2）[Mn（CO）3] 2是由于最初存在于N2 S2 4-口袋中的M的损失导致的，被质子化所取代在酰胺氮上生成H2 ema2-。因此，ema配体已将其配位模式从容纳单一金属的N2 S2-4腔切换为双硫H2 ema2-，在Mn-μ-S-CH2-CO-五元环内桥接硫和羧酰胺氧。通过锌离子原位金属模板化可定量获得Mn2产物。通过计算研究，我们比较了“线性” ema4-构型，冷冻在单个金属周围“紧密环”中的ema4-构型，以及与H2 ema2-的“较松散”折叠（这是双核的最佳排列）的构象。XRD分子结构在固态的酰胺氮质子上显示出广泛的H键。

更新日期：2020-01-22

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