Comparative Spectroscopic Studies of Iron(III) and Manganese(III) Salen Complexes Having a Weakly Coordinating Triflate Axial Ligand

Kurahashi Takuya; Fujii Hiroshi

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Comparative Spectroscopic Studies of Iron(III) and Manganese(III) Salen Complexes Having a Weakly Coordinating Triflate Axial Ligand

机译：铁（III）和锰（III）锰（III）的比较光谱研究，其具有弱协调的Triflate轴配体

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We thoroughly compared spectroscopic and magnetic properties of mononuclear iron(III) and manganese(III) complexes with symmetric and nonsymmetrical salen ligands, in order to investigate the relation between spectroscopic properties and electronic structures. Magnetic susceptibility and dual-mode electron paramagnetic resonance data show the assignment of [Fe-III(salen)(OTf)] and [Mn-III(salen)(OTf)] as high-spin S = 5/2 and S = 2 electronic configurations, respectively, irrespective of the electron-donating properties and symmetry of the salen ligand. Further insights into electronic structures of central metal are obtained from H-2 NMR spectra of selectively deuterated complexes, in which [Fe-III(salen)(OTf)] and [Mn-III(salen)(OTf] exhibit well-resolved paramagnetic NMR signals of quite different shift patterns, due to the presence or absence of the unpaired electron in the d(x2-y2) orbital expected for S = 5/2 iron(III) or S = 2 manganese(III) centers.

机译：我们彻底比较了单核铁（III）和锰（III）络合物的光谱和磁性，以探讨光谱性能和电子结构之间的关系。磁化率和双模电子顺磁共振数据显示[Fe-III（Salen）（OTF）]和[Mn-III（Salen）（OTF）]作为高旋转S = 5/2和S = 2的分配电子配置分别，无论盐配体的电子捐赠性能和对称性。从选择性氘代络合物的H-2 NMR光谱获得进一步的中央金属结构的见解，其中[Fe-III（Salen）（OTF）]和[Mn-III（Salen）（OTF]表现出良好分辨的顺磁性由于S = 5/2铁（III）或S = 2锰（III）中心的D（x2-y2）轨道中的未配对电子的存在或不存在的未配对电子的存在或不存在的换档模式的NMR信号。

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《Bulletin of the Chemical Society of Japan》 |2012年第9期|共8页
作者
Kurahashi Takuya; Fujii Hiroshi;
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Natl Inst Nat Sci Inst Mol Sci Okazaki Aichi 4448787 Japan;

Natl Inst Nat Sci Inst Mol Sci Okazaki Aichi 4448787 Japan;

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正文语种 eng
中图分类化学;
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1. Comparative Spectroscopic Studies of Iron(III) and Manganese(III) Salen Complexes Having a Weakly Coordinating Triflate Axial Ligand [J] . Kurahashi Takuya, Fujii Hiroshi Bulletin of the Chemical Society of Japan . 2012,第9期

机译：铁（III）和锰（III）锰（III）的比较光谱研究，其具有弱协调的Triflate轴配体
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Comparative Spectroscopic Studies of Iron(III) and Manganese(III) Salen Complexes Having a Weakly Coordinating Triflate Axial Ligand

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