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A [2Fe-1S] Complex That Affords Access to Bimetallic and Higher-Nuclearity Iron-Sulfur Clusters.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-06-19 , DOI: 10.1021/acs.inorgchem.9b01212 Daniel E DeRosha 1 , Nicholas A Arnet 1 , Brandon Q Mercado 1 , Patrick L Holland 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-06-19 , DOI: 10.1021/acs.inorgchem.9b01212 Daniel E DeRosha 1 , Nicholas A Arnet 1 , Brandon Q Mercado 1 , Patrick L Holland 1
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Small, coordinatively unsaturated iron-sulfur clusters are conceived as building blocks for the diverse set of shapes of iron-sulfur clusters in biological and synthetic chemistry. Here we describe a synthetic method for preparing [2Fe-1S] clusters containing two iron(II) ions, which are supported by a relatively unhindered β-diketiminate supporting ligand. The [2Fe-1S] cluster can be isolated in the presence of trimethylphosphine, and the compound with one PMe3 on each iron(II) ion has been crystallographically characterized. The PMe3 ligands may be removed with B(C6F5)3 to give a spectroscopically characterized species with solvent ligands. This species is a versatile synthon for [2Fe-2S], [4Fe-3S], and [10Fe-8S] clusters. Crystallographic characterization of the 10Fe cluster shows that it has all iron(II) ions, and the core has two [4Fe-4S] cubes that share a face in a novel arrangement. This cluster also has two iron sites that are coordinated to solvent donors, suggesting the potential for using this type of cluster for reactivity in the future.
中文翻译:
一种[2Fe-1S]络合物,可承受双金属和高核铁-硫簇的访问。
小型,配位不饱和的铁硫簇被认为是生物化学和合成化学中各种形状的铁硫簇形状的基础。在这里,我们描述了一种制备[2Fe-1S]团簇的合成方法,该团簇包含两个铁(II)离子,这些团簇由相对不受阻碍的β-二酮支持配体支撑。可以在三甲基膦的存在下分离[2Fe-1S]簇,并且对每个铁(II)离子上带有一个PMe3的化合物进行了晶体学表征。可以用B(C6F5)3除去PMe3配体,从而得到具有溶剂配体的光谱表征物质。该物种是[2Fe-2S],[4Fe-3S]和[10Fe-8S]簇的通用合成子。10Fe团簇的晶体学表征表明,它具有所有的铁(II)离子,核心有两个[4Fe-4S]立方体,它们以新颖的排列方式共享一个面孔。该团簇还具有两个与溶剂供体协调的铁位点,这表明将来有可能使用这种类型的团簇进行反应。
更新日期:2019-06-19
中文翻译:

一种[2Fe-1S]络合物,可承受双金属和高核铁-硫簇的访问。
小型,配位不饱和的铁硫簇被认为是生物化学和合成化学中各种形状的铁硫簇形状的基础。在这里,我们描述了一种制备[2Fe-1S]团簇的合成方法,该团簇包含两个铁(II)离子,这些团簇由相对不受阻碍的β-二酮支持配体支撑。可以在三甲基膦的存在下分离[2Fe-1S]簇,并且对每个铁(II)离子上带有一个PMe3的化合物进行了晶体学表征。可以用B(C6F5)3除去PMe3配体,从而得到具有溶剂配体的光谱表征物质。该物种是[2Fe-2S],[4Fe-3S]和[10Fe-8S]簇的通用合成子。10Fe团簇的晶体学表征表明,它具有所有的铁(II)离子,核心有两个[4Fe-4S]立方体,它们以新颖的排列方式共享一个面孔。该团簇还具有两个与溶剂供体协调的铁位点,这表明将来有可能使用这种类型的团簇进行反应。