二茂铁邻苯醌亚锡(IV)电子转移配合物。

Ferrocene-o-benzosemiquinonato tin(IV) electron-transfer complexes.

机构信息

G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinina str., 603950, Nizhniy Novgorod, GSP-445, Russia.

出版信息

Inorg Chem. 2013 May 6;52(9):5284-9. doi: 10.1021/ic400713p. Epub 2013 Apr 8.

DOI:10.1021/ic400713p

PMID:23565572

Abstract

The interaction of ferrocene with tin(IV) o-benzosemiquinonato complexes in acetonitrile results in a reversible electron transfer (ET) from ferrocene to the redox-active ligand with the formation of electron-transfer complexes (3,6-Cat)SnBr3 Cp2Fe (1) and (3,6-Cat)(3,6-SQ)SnCl2 Cp2Fe (2), where 3,6-Cat is the 3,6-di-tert-butyl-catecholate dianion and 3,6-SQ is the 3,6-di-tert-butyl-o-benzosemiquinonato radical anion. The ET process and the solvent effect in the system "ferrocene-o-benzosemiquinonato tin(IV) complexes" were investigated on the basis of a combination of spectroscopic and X-ray diffraction methods. The molecular structures of 1 and 2 were confirmed by X-ray analysis. Complex 2 demonstrates the ferromagnetic coupling in the linear chain alternating ···D(+•)A(-•)D(+•)A(-•)··· motif.

摘要

在乙腈中，二茂铁与锡（IV）邻苯醌半醌配合物的相互作用导致从二茂铁到氧化还原活性配体的可逆电子转移（ET），形成电子转移配合物(3,6-Cat)SnBr3 Cp2Fe（1）和(3,6-Cat)(3,6-SQ)SnCl2 Cp2Fe（2），其中 3,6-Cat 是 3,6-二叔丁基儿茶酚二阴离子，3,6-SQ 是 3,6-二叔丁基邻苯醌半醌自由基阴离子。基于光谱和 X 射线衍射方法的组合，研究了体系“二茂铁-邻苯醌锡（IV）配合物”中的 ET 过程和溶剂效应。1 和 2 的分子结构通过 X 射线分析得到证实。配合物 2 在交替的···D(+)A(-•)D(+)A(-•)···模体中表现出铁磁耦合。