Structural characterization of manganese and iron complexes with methylated derivatives of bis(2-pyridylmethyl)-1,2-ethanediamine reveals unanticipated conformational flexibility

Coates C.M.; Hagan K.; Mitchell C.A.; Gorden J.D.; Goldsmith C.R.

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Structural characterization of manganese and iron complexes with methylated derivatives of bis(2-pyridylmethyl)-1,2-ethanediamine reveals unanticipated conformational flexibility

机译：锰和铁配合物的双（2-吡啶甲基）-1，2-乙二胺甲基化衍生物的结构表征显示出意想不到的构象灵活性

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Iron and manganese complexes with derivatives of bis(2-pyridylmethyl)-1,2- ethanediamine (bispicen) have previously been found to be efficient catalysts for hydrocarbon oxygenation. Methylation can potentially impact the conformation of the ligand around the metal center and the electronic character of the bound metal ion; each of these, in turn, impacts reactivity. Reported are mononuclear manganese(ii) and iron(ii) compounds with bispicen and five increasingly methylated derivatives. The extent and sites of methylation strongly impact the optical and electrochemical properties of the manganese and iron complexes. Increased methylation is correlated with more positive M(iii/ii) reduction potentials. Structural analysis of the Mn(ii) series reveals two ligand conformations that have never been observed for the bispicen framework, cis-β and trans, in addition to the common cis-α conformation. 1H NMR spectra of the structurally characterized iron compounds are consistent with mixtures of these conformers, suggesting that bispicen coordination is both more flexible and more dynamic than previously thought.

机译：先前已发现具有双（2-吡啶基甲基）-1，2-乙二胺（双吡啶）衍生物的铁和锰配合物是烃氧合的有效催化剂。甲基化可能会影响金属中心周围的配体构象和结合的金属离子的电子特性;这些因素反过来都会影响反应性。报告的是单核锰（ii）和铁（ii）化合物，带有双比辛和五个甲基化程度更高的衍生物。甲基化的程度和位点强烈影响锰和铁配合物的光学和电化学性质。增加的甲基化与更积极的M（iii / ii）还原潜力相关。 Mn（ii）系列的结构分析表明，除了常见的顺式α构象外，对于双峰构架从未观察到的两个配体构象为顺式β和反式。结构上表征的铁化合物的1 H NMR谱图与这些构象异构体的混合物一致，这表明二picen配位比以前认为的更灵活，更动态。

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《Dalton transactions: An international journal of inorganic chemistry》 |2011年第16期|共11页
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Coates C.M.; Hagan K.; Mitchell C.A.; Gorden J.D.; Goldsmith C.R.;
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1. Structural characterization of manganese and iron complexes with methylated derivatives of bis(2-pyridylmethyl)-1,2-ethanediamine reveals unanticipated conformational flexibility [J] . Coates C.M., Hagan K., Mitchell C.A., Dalton transactions: An international journal of inorganic chemistry . 2011,第16期

机译：锰和铁配合物的双（2-吡啶甲基）-1，2-乙二胺甲基化衍生物的结构表征显示出意想不到的构象灵活性
2. Syntheses,Characterization and Reactivity of Iron(II),Nickel(II),Copper(II) and Zinc(II)Complexes of the Ligand N,N,N',N'-Tetrakis(2-pyridylmethyl)-benzene-1,3-diamine(1,3-tpbd)and Its Phenol Derivative 2,6-Bis[bis(2-pyridylmethyl)amino]-p-cresol(2,6 [J] . Simon Foxon, Jing-Yuan Xu, Sabrina Turba European journal of inorganic chemistry . 2007,第3期

机译：N，N，N'，N'-四（2-吡啶基甲基）-苯-1， 3-二胺（1,3-tpbd）及其苯酚衍生物2,6-双[双（2-吡啶基甲基）氨基]-对甲酚（2,6
3. Complexation equilibrium between iron(III) and N,N '-bis(2-hydroxyphenylmethyl)N,N '-bis(2-pyridylmethyl)-1,2-ethanediamine [J] . Hirayama N., Kuzuya N., Kubono K., Analusis: Chimie Analytique - Methodes Physiques d'Analyse . 1998,第9期

机译：铁（III）与N，N'-双（2-羟基苯基甲基）N，N'-双（2-吡啶基甲基）-1,2-乙二胺之间的络合平衡
4. Synthesis and Characterization of Transition Metal Complexes of 1,2-Bis(3,5-dimethylpyrazol-1 -yl)-1,2-ethanediol [C] . Galyna A. Anosova, Vladislava V. Matveevskaya, Nurgul A. Pirmanova International Conference for Young Scientists "High Technology: Research and Applications" . 2016

机译：1,2-双（3,5-二甲基吡唑-1-基）-1,2-乙二醇的过渡金属配合物的合成与表征
5. Structural characterization of iron(III) tris(2-pyridylmethyl)amine complexes with the formulas (iron(TPA)X(2))(chlorine tetroxide) and ((iron(TPA)X)(2)O)(chlorine tetroxide)(2). [D] . Xue, Jia. 1996

机译：具有以下结构式的三价铁（III）三（2-吡啶基甲基）胺配合物的结构表征：铁（TPA）X（2））（四氧化氯）和（（铁（TPA）X）（2）O）（四氧化氯）（2）。
6. Synthesis structural studies and oxidation catalysis of the manganese(II) iron(II) and copper(II) complexes of a 2-pyridylmethyl pendant armed side-bridged cyclam [O] . Anthony D. Shircliff, Kevin R. Wilson, Desiray J. Cannon, -1

机译：2-吡啶基甲基悬挂侧桥环己酰胺的锰（II）铁（II）和铜（II）配合物的合成结构研究和氧化催化
7. Solvent Extraction of Alkaline Earth Metal Ions Using N,N'-bis(2-hydroxyphenylmethyl)-N,N'-bis(2-pyridylmethyl)-1,2-ethanediamine Derivative. [O] . Hisao KOKUSEN, Yu KOMATSU, Koji KUBONO, 2003

机译：使用N，N'-BIS（2-羟基苯甲基）-N，N'-Bis（2-吡啶基甲基）-1,2-乙二胺衍生物的溶剂萃取碱土金属离子。
8. Coordination Chemistry of Bidentate Difluorophosphines. 3. Complexes of 1,2-Bis(Difluorophosphino) Cyclohexane with Molybdenum(0), Manganese(I), and Iron(0). [R] . Gallup, D. L., Morse, J. G. 1978

机译：双齿二氟膦的配位化学。 3. 1,2-双（二氟膦基）环己烷与钼（0），锰（I）和铁（0）的配合物。

Structural characterization of manganese and iron complexes with methylated derivatives of bis(2-pyridylmethyl)-1,2-ethanediamine reveals unanticipated conformational flexibility

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