Lindhorst Anja C, Kaspar Manuel, Altmann Philipp J, Pöthig Alexander, Kühn Fritz E
Molecular Catalysis, Catalysis Research Center and Department of Chemistry, Technical University of Munich, Lichtenbergstr. 4, D-85747 Garching bei München, Germany.
Dalton Trans. 2018 Feb 6;47(6):1857-1867. doi: 10.1039/c7dt04774f.
The syntheses of a novel hydroxyl-functionalized tetradentate NHC/pyridine hybrid ligand and the corresponding Ag(i) and Fe(ii) complexes are presented. Spectroscopic and X-ray diffraction techniques are used for structural investigations and cyclic voltammetry measurements reveal interesting electronic properties. Transmetalation of the trinuclear Ag(i) complex (C1) yields a mononuclear and a dinuclear iron(ii) bis(NHC) complex (C2 and C3), which can be separated by stepwise precipitation. The former is isostructural to iron(ii) bis(NHC) complex A, which is a versatile oxidation catalyst. Furthermore, suitable conditions for esterification reactions of the ligand precursor and iron(ii) bis(NHC) complex (C2) have been established, demonstrating the utility of the hydroxyl functionality for immobilization and derivatization purposes.
本文介绍了一种新型羟基官能化四齿NHC/吡啶杂化配体以及相应的Ag(i)和Fe(ii)配合物的合成。采用光谱和X射线衍射技术进行结构研究，循环伏安法测量揭示了有趣的电子性质。三核Ag(i)配合物(C1)的金属转移反应生成了单核和双核铁(ii)双(NHC)配合物(C2和C3)，它们可以通过分步沉淀分离。前者与铁(ii)双(NHC)配合物A同构，后者是一种通用的氧化催化剂。此外，还建立了配体前体和铁(ii)双(NHC)配合物(C2)酯化反应的合适条件，证明了羟基官能团在固定化和衍生化方面的实用性。
