Half-sandwich metal complexes are of considerable interest in medicinal, material, and nanomaterial chemistry. The design of libraries of such complexes with particular reactivity and properties is therefore a major quest. Here, we report the unique and peculiar reactivity of eight apparently 16-electron half-sandwich metal (ruthenium, osmium, rhodium, and iridium) complexes based on benzene-1,2-dithiolato and 3,6-dichlorobenzene-1,2-dithiolato chelating ligands. These electron-deficient complexes do not react with electron-donor pyridine derivatives, even with the strong σ-donor 4-dimethylaminopyridine (DMAP) ligand. The Ru, Rh, and Ir complexes accept electrons from the triphenylphosphine ligand (σ-donor, π-acceptor), whilst the Os complexes were found to be the first examples of non-electron-acceptor electron-deficient metal complexes. We rationalised these unique properties by a combination of experimental techniques and DFT/TDFT calculations. The synthetic versatility offered by this family of complexes, the low reactivity at the metal center, and the facile functionalisation of the non-innocent benzene ligands is expected to allow the synthesis of libraries of pseudo electron-deficient half-sandwich complexes with unusual properties for a broad range of applications.

中文翻译：

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伪电子不足的有机金属：对给电子配体的反应性有限。

半夹心金属络合物在药物，材料和纳米材料化学领域具有相当大的兴趣。因此，设计具有特定反应性和性质的此类复合物的库是主要的追求。在这里，我们报道了基于苯-1,2-二硫代拉托和3,6-二氯苯-1,2-二硫lato螯合配体。这些电子不足的络合物即使与强大的σ-供体4-二甲基氨基吡啶（DMAP）配体也不会与电子-供体吡啶衍生物反应。Ru，Rh和Ir络合物从三苯膦配体（σ供体，π受体）接受电子，而Os络合物被发现是非电子受体缺电子的金属络合物的第一个实例。我们通过结合实验技术和DFT / TDFT计算来合理化这些独特的属性。该配合物家族提供的合成多功能性，在金属中心的低反应性以及非纯苯配体的简便官能化，有望合成具有非常规性质的伪电子缺陷型半三明治配合物文库。广泛的应用。