Synthesis, Dioxygen Affinities and Biomimetic Catalytic Oxidation Performance of Crown Ether-tethered Schiff Base Transition-Metal Complexes

Journal of Supramolecular Chemistry Pub Date : 2002-12-01 DOI:10.1016/j.jsupra.2004.02.001

Wei Zeng , Zhihua Mao , Xingyao Wei , Jianzhang Li , Zhou Hong , Shengying Qin

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引用次数: 14

Abstract

Mono-Schiff bases containing crown ether ring (HL¹, HL², HL³ and HL⁴) and their transition-metal complexes were synthesized and characterized by ¹H NMR, IR, MS spectra and elemental analysis. The crystal structures of HL¹, HL³ and CoL₂¹ were determined from X-ray diffraction data. The oxygenation constants (Ko₂) of Schiff-base Co (II) complexes were measured over a range of −5 °C to 25 °C, and the values of ΔH⁰ and ΔS⁰ were also calculated based on Ko₂. In the presence of Mn (III) Schiff base complexes, the biomimetic catalytic oxidation for styrene to benzalhyde was carried out at 100% selectivity. Compared with the uncrowned analogue, the influence of crown ring and its bonding pattern, the distance between the coordination center and crown ring on the dioxygen affinities and biomimetic catalytic oxidation performance of the crowned Schiff base complexes were observed.

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冠醚束缚希夫碱过渡金属配合物的合成、二氧亲和性及其仿生催化氧化性能

合成了含有冠醚环的单希夫碱（HL1、HL2、HL3和HL4）及其过渡金属配合物，并用1H NMR、IR、MS和元素分析对其进行了表征。根据X射线衍射数据确定了HL1、HL3和CoL21的晶体结构。在−5°C至25°C范围内测量了席夫碱Co（II）配合物的氧化常数（Ko2），并基于Ko2计算了ΔH0和ΔS0的值。在Mn（III）Schiff碱配合物存在下，苯乙烯的仿生催化氧化反应以100%的选择性进行。与未加冕的类似物相比，观察了冠环及其键合模式、配位中心与冠环之间的距离对加冕的席夫碱配合物的氧亲和力和仿生催化氧化性能的影响。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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Journal of Supramolecular Chemistry

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