Ligand Control of Manganese Telluride Molecular Cluster Core Nuclearity,Inorganic Chemistry

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Ligand Control of Manganese Telluride Molecular Cluster Core Nuclearity
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2015-08-26 00:00:00 , DOI: 10.1021/acs.inorgchem.5b01020
Bonnie Choi ₁ , Daniel W. Paley ₁ , Theo Siegrist _{2,

3} , Michael L. Steigerwald ₁ , Xavier Roy ₁

Affiliation

We report the synthesis, structural diversity, and chemical behavior of a family of manganese telluride molecular clusters whose charge-neutral cores are passivated by two-electron donor ligands. We describe three different core structures: a cubane-type Mn₄Te₄, a prismane Mn₆Te₆, and a dicubane Mn₈Te₈. We use various trialkylphosphines and N-heterocyclic carbenes (NHCs) as surface ligands and demonstrate that the formation of the different cluster core structures is controlled by the choice of ligand: bulky ligands such as PⁱPr₃, PCy₃, or ⁱPr₂NHC (ⁱPr₂NHC = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) form the cubane-type core, while the smaller PMe₃ produces the prismane core. The intermediate-sized PEt₃ produces both cubane and prismane species. These manganese telluride molecular clusters are labile, and the capping phosphines can be replaced by stronger ligands, while the internal core structure of the cluster remains intact. The interplay of structural diversity and ligand versatility and lability makes these clusters potentially useful building blocks for the assembly of larger aggregates and extended structures. We demonstrate the simplest prototype of these solid-forming reactions: the direct coupling of two Mn₄Te₄(ⁱPr₂NHC)₄ units to form the dicubane Mn₈Te₈(ⁱPr₂NHC)₆. We also postulate the prismatic Mn₆Te₆ as the common ancestor of both Chevrel-type M₆E₈ and octanuclear rhombododecahedral M₈E₆ molecular clusters (M = transition metal and E = chalcogen), and we discuss the core structure of our molecular clusters as recognizable building units for the zinc blende and the hypothetical wurtzite lattices of MnTe.

中文翻译：

碲化锰分子簇核心核的配体控制

我们报告了锰碲化物分子簇家族的合成，结构多样性和化学行为，其电荷中性核心被两电子供体配体钝化。我们描述了三种不同的核心结构：古巴型Mn ₄ Te ₄，三氮烷Mn ₆ Te ₆和二茂锰Mn ₈ Te ₈。我们使用各种三烷基膦和N-杂环卡宾（NHCs）作为表面配体，并证明不同簇核心结构的形成受配体的选择控制：庞大的配体，如P ⁱ Pr ₃，PCy ₃或ⁱ Pr ₂ NHC（^我镨₂ NHC = 1,3-二异丙基-4,5-二甲基咪唑烷-2-亚基）形成立方烷型芯，而较小的PME₃产生棱晶烷核。中等尺寸的PEt₃既可以生产古巴也可以生产三棱烷。这些碲化锰分子簇不稳定，并且封端膦可以被更强的配体取代，而簇的内部核心结构则保持完整。结构多样性，配体的多功能性和不稳定性之间的相互作用使这些簇潜在地成为组装较大的聚集体和扩展结构的有用构建基块。我们展示了这些固相反应的最简单原型：两个Mn₄ Te₄（ⁱ Pr₂ NHC）_4个单位形成二茂铁Mn₈ Te₈（ⁱ Pr₂ NHC）₆。我们还假设棱形的Mn₆ Te₆是Chevrel型M₆ E₈和八角形菱形十二面体M₈ E₆分子簇（M =过渡金属和E =硫族元素）的共同祖先，我们讨论了我们的核心结构分子簇作为锌共混物和MnTe假想纤锌矿晶格的可识别构建单元。

更新日期：2015-08-26

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