Reactivity of Unsupported Transition Metal-Aluminyl Complexes: A Nucleophilic TM-Al Bond,Inorganic Chemistry

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Reactivity of Unsupported Transition Metal-Aluminyl Complexes: A Nucleophilic TM-Al Bond
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-06-15 , DOI: 10.1021/acs.inorgchem.2c01789
Xueying Guo ₁ , Tilong Yang ₁ , Yichi Zhang ₁ , Fu Kit Sheong ₁ , Zhenyang Lin ₁

Affiliation

Despite the long history of research in transition metal (TM) complexes, the study of TM-aluminyl complexes is still in its early stage of development. It is expected that the presence of an electropositive Al donor atom would open up new possibilities in TM complex reactivity, and indeed TM-aluminyl has shown an early sign of success in small-molecule activation. On the other hand, the existing reports on TM-aluminyl reactivity are often explained to readers with different understanding on individual cases, and a general picture of TM-aluminyl reactivity is still not available. In this work, we have attempted to provide a systematic picture to explain some early explorations in this field, specifically a series of recently reported heteroallene insertion reactions involving unsupported TM-aluminyl complexes. Through density functional theory calculations of a number of TM-aluminyl complexes, covering both Au and Cu centers, we found that their reactivity against heteroallenes (including CO₂ and carbodiimides) is mostly based on the strong nucleophilicity of the TM–Al σ-bond.

中文翻译：

无载体过渡金属-铝基配合物的反应性：亲核 TM-Al 键

尽管过渡金属（TM）配合物的研究历史悠久，但对TM-铝基配合物的研究仍处于早期发展阶段。预计正电性 Al 供体原子的存在将为 TM 复合物反应性开辟新的可能性，实际上 TM-aluminyl 已显示出小分子活化成功的早期迹象。另一方面，现有的关于 TM-aluminyl 反应性的报道往往是针对个别情况向不同理解的读者解释，目前还没有 TM-aluminyl 反应性的总体图景。在这项工作中，我们试图提供一个系统的图片来解释该领域的一些早期探索，特别是最近报道的一系列涉及无载体的 TM-铝基配合物的杂丙二烯插入反应。₂和碳二亚胺）主要基于TM-Al σ键的强亲核性。

更新日期：2022-06-15

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