Meyer Steffen, Krahe Oliver, Kupper Claudia, Klawitter Iris, Demeshko Serhiy, Bill Eckhard, Neese Frank, Meyer Franc
Institut für Anorganische Chemie, Georg-August-Universität Göttingen , Tammannstraße 4, 37077 Göttingen, Germany.
Max Planck Institute for Chemical Energy Conversion , Stiftstraße 34-36, 45470 Mülheim an der Ruhr, Germany.
Inorg Chem. 2015 Oct 19;54(20):9770-6. doi: 10.1021/acs.inorgchem.5b01446. Epub 2015 Oct 7.
A disulfide-bridged diiron complex with [Fe-S-S-Fe] core, which represents an isomer of the common biological [2Fe-2S] ferredoxin-type clusters, was synthesized using strongly σ-donating macrocyclic tetracarbene capping ligands. Though the complex is quite labile in solution, single crystals were obtained, and the structure was elucidated by X-ray diffraction. The electron-rich iron-sulfur core is found to show rather unusual magnetic and electronic properties. Experimental data and density functional theory studies indicate extremely strong antiferromagnetic coupling (-J > 800 cm(-1)) between two low-spin iron(III) ions via the S2(2-) bridge, and the intense near-IR absorption characteristic for the [Fe-S-S-Fe] core was assigned to a S → Fe ligand-to-metal charge transfer transition.
一种具有[Fe-S-S-Fe]核心的二硫桥连二铁配合物，它是常见生物[2Fe-2S]铁氧化还原蛋白型簇的一种异构体，使用强σ供体大环四卡宾封端配体合成。尽管该配合物在溶液中相当不稳定，但仍获得了单晶，并通过X射线衍射阐明了其结构。发现富电子的铁硫核心表现出相当不寻常的磁性和电子性质。实验数据和密度泛函理论研究表明，两个低自旋铁(III)离子通过S2(2-)桥之间存在极强的反铁磁耦合(-J > 800 cm(-1))，并且[Fe-S-S-Fe]核心强烈的近红外吸收特征被归因于S→Fe配体到金属的电荷转移跃迁。
