TAUTOMERIC CATECHOLATE-SEMIQUINONE INTERCONVERSION VIA METAL-LIGAND ELECTRON-TRANSFER - STRUCTURAL, SPECTRAL, AND MAGNETIC-PROPERTIES OF (3,5-DI-TERT-BUTYLCATECHOLATO)-(3,5-DI-TERT-BUTYLSEMIQUINONE)(BIPYRIDYL)COBALT(III), A COMPLEX CONTAINING MIXED-VALENCE ORGANIC-LIGANDS
TAUTOMERIC CATECHOLATE-SEMIQUINONE INTERCONVERSION VIA METAL-LIGAND ELECTRON-TRANSFER - STRUCTURAL, SPECTRAL, AND MAGNETIC-PROPERTIES OF (3,5-DI-TERT-BUTYLCATECHOLATO)-(3,5-DI-TERT-BUTYLSEMIQUINONE)(BIPYRIDYL)COBALT(III), A COMPLEX CONTAINING MIXED-VALENCE ORGANIC-LIGANDS
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DOI：
10.1021/ja00535a021
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发表时间：
1980-01-01
影响因子：
15
通讯作者：
PIERPONT, CG
中科院分区：
文献类型：
--
作者：
BUCHANAN, RM;PIERPONT, CG
在甲苯溶液中，母体Co(II)与联吡啶反应生成联吡啶四聚物[Co(3，5-DBSQ)2]4。内部配位球内的结构特征与Co(III)金属中心一致。其中一个独立的苯二酚配体配位为半喹酮，另一个配位为儿茶酚。在甲苯溶液中，磁性、电子顺磁共振、核磁共振和光谱实验结果表明，Co(II)物种Co(3，5-DBSQ)2(Bpy)与固相Co(III)形式Co(3，5-DBCat)(3，5-DBSQ)(Bpy)之间存在平衡。这两种形式的络合物通过金属离子和其中一种苯醌配体之间的电子转移而联系在一起。
The bipyridyl adduct of tetrameric [Co (3, 5-DBSQ) 2] 4 has been formed by treating the parent Co (II) complex with bipyridine in toluene solution. Structural features within the inner coordination sphere are consistent with a Co (III) metal center. One of the independent quinone ligands is coordinated as a semiquinone and the other as a catecholate. In toluene solution the results of magnetic, EPR, NMR, and spectral experiments suggest an equilibrium between a Co (II) species Co (3, 5-DBSQ) 2 (bpy) and the Co (III) form found inthe solid state, Co (3, 5-DBCat)(3, 5-DBSQ)(bpy). These two forms of the complex are related by the transfer of an electron between the metal ion and one of the quinone ligands.