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利用肼将二茂铁与铼(羰基)连接:一种模块化方法。

Using Hydrazine to Link Ferrocene with Re(CO): A Modular Approach.

作者信息

Chanawanno Kullapa, Rhoda Hannah M, Hasheminasab Abed, Crandall Laura A, King Alexander J, Herrick Richard S, Nemykin Victor N, Ziegler Christopher J

机构信息

Department of Chemistry, University of Akron, OH 44325-3601, USA.

Department of Chemistry & Biochemistry, University of Minnesota Duluth, Duluth, MN 55812, USA.

出版信息

J Organomet Chem. 2016 Sep 1;818:145-153. doi: 10.1016/j.jorganchem.2016.06.004. Epub 2016 Jun 7.

Abstract

Acetyl ferrocene and diacetyl ferrocene both readily react with an excess of hydrazine to afford the corresponding hydrazone compounds. These compounds can then be linked to Re(CO) via a metal-mediated Schiff base reaction, resulting in a series of ferrocene-Re(CO) conjugates with different stoichiometries. Conjugates with 1:1, 1:2, and 2:1 ferrocene: Re(CO) ratios can be produced via this "modular" type synthesis approach. Several examples of these conjugates were structurally characterized, and their spectroscopic, electrochemical, and spectroelectrochemical behaviors were investigated. The electronic structures of these compounds were also probed using DFT and TDDFT calculations.

摘要

乙酰基二茂铁和二乙酰基二茂铁都能与过量的肼迅速反应,生成相应的腙化合物。然后,这些化合物可以通过金属介导的席夫碱反应与Re(CO)相连,生成一系列具有不同化学计量比的二茂铁-Re(CO)共轭物。通过这种“模块化”合成方法,可以制备出二茂铁与Re(CO)比例为1:1、1:2和2:1的共轭物。对这些共轭物的几个实例进行了结构表征,并研究了它们的光谱、电化学和光谱电化学行为。还使用密度泛函理论(DFT)和含时密度泛函理论(TDDFT)计算对这些化合物的电子结构进行了探究。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ad5d/5421566/6adbca02e7b4/nihms795866f1.jpg

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