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通过现代光谱研究确定金属/配体相互作用之间的配位稳定性:含环状配体的有机骨架钴(II)配合物的红外光谱、电子光谱、电子顺磁共振光谱和循环伏安法

Coordination stability between metal/ligands interaction by modern spectroscopic studies: IR, electronic, EPR and cyclic voltammetry of cobalt(II) complexes with organic skeleton containing cyclic ligands.

作者信息

Chandra Sulekh, Kumar Rajiv, Singh Rajeev, Jain Akash Kr

机构信息

Department of Chemistry, Zakir Husain College (University of Delhi), Jawahar Lal Nehru Marg, New Delhi 110002, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2006 Nov;65(3-4):852-8. doi: 10.1016/j.saa.2006.01.005. Epub 2006 May 6.

Abstract

A comparative investigation of the interaction of two pyrrole-substituted, mixed oxygen and nitrogen donor, macrocycles ligands have been designed and their coordination interaction with cobalt(II) is studied. Cobalt(II) salts combine with a tetradentate and hexadentate macrocyclic nitrogen/oxygen donor ligands and formed novel cobalt(II) complexes which are characterized by elemental analysis, molar conductance, magnetic moments, mass, (1)H NMR, IR, electronic and EPR spectral studies. At the room temperature magnetic moment for cobalt(II) complexes lie in the range 4.70-5.01BM, which is higher than the spin-only value. All the complexes are high-spin type and have three unpaired electrons. Therefore, the electronic confutation and the splitting of the orbital will be t(2g)(5)eg(2). The electrochemical behaviour of the cobalt(II) complexes, the Co(III)/Co(II) couple are observed. Their positive potential indicates that metal in lower oxidation state is strongly bound to these ligands. The difference between the potential of the anodic peak and cathodic peak remains constant in all complexes. Also, the ratio between the cathodic peak current and square root of the scan rate is practically constant for the studied complexes.

摘要

对两种吡咯取代的、混合氧和氮供体的大环配体的相互作用进行了比较研究,并设计了这些配体,同时研究了它们与钴(II)的配位相互作用。钴(II)盐与一种四齿和六齿大环氮/氧供体配体结合,形成了新型钴(II)配合物,通过元素分析、摩尔电导率、磁矩、质谱、(1)H NMR、红外光谱、电子光谱和电子顺磁共振光谱研究对其进行了表征。在室温下,钴(II)配合物的磁矩在4.70 - 5.01BM范围内,高于仅自旋值。所有配合物均为高自旋型,具有三个未成对电子。因此,电子组态和轨道分裂将为t(2g)(5)eg(2)。观察到了钴(II)配合物Co(III)/Co(II)电对的电化学行为。它们的正电位表明较低氧化态的金属与这些配体强烈结合。在所有配合物中,阳极峰和阴极峰电位之间的差值保持恒定。此外,对于所研究的配合物,阴极峰电流与扫描速率平方根的比值实际上是恒定的。

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