三芳基铝对带有多功能卡宾配体的 Ni(0) 中心周围电子和空间环境的可逆调节,Journal of the American Chemical Society

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三芳基铝对带有多功能卡宾配体的 Ni(0) 中心周围电子和空间环境的可逆调节
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-07-19 , DOI: 10.1021/jacs.3c06267
Yasuhiro Yamauchi ₁ , Yutaka Mondori ₁ , Yuta Uetake _{1,

2} , Yasuo Takeichi ₃ , Takahiro Kawakita ₁ , Hidehiro Sakurai _{1,

2} , Sensuke Ogoshi ₁ , Yoichi Hoshimoto _{1,

4}

Affiliation

设计和调节金属中心周围的电子和空间环境是使用有机金属化合物的广泛化学领域中的一个关键问题。在此，我们证明了路易斯酸介导的镍（0）中心周围空间环境的可逆膨胀、收缩和转变，该中心带有N-氧化膦取代的N-杂环卡宾（以下称为（S）PoxIms）。四面体 ( syn -κ- C , O -(S)PoxIm)Ni(CO) ₂和 Al(C ₆ F ₅ ) ₃之间的反应顺利地提供了异双金属 Ni/Al 物种，例如三角平面 {κ- C -Ni( CO) ₂ }(μ- anti -(S)PoxIm){κ- O -Al(C ₆ F ₅ ) _{3 } 通过}N-氧化膦部分的络合诱导旋转，同时添加 4-二甲基氨基吡啶产生以前的镍配合物的定量再生。(SPoxIm)Ni(η ² :η ² -二苯基二乙烯基硅烷)和{κ- C -Ni(η ² :η ^{2 -}二烯)}(μ- anti -SPoxIm){κ- O -Al( C ₆ F ₅ ) ₃ } 通过Al(C ₆ F ₅ ) ₃的配位和解离。通过这种路易斯酸介导的互变，Ni(0)中心周围空间的形状和大小发生了巨大的变化。此外，上述羰基配合物的多核NMR、IR和XAS分析阐明了Ni中心电子态变化的细节；即，异质双金属Ni/Al物质中Ni原子和CO配体之间的电子离域得到有效增强。因此，除了广为接受的路易斯碱介导的配体取代方法之外，这项工作中提出的结果还提供了一种可逆调节有机金属配合物的电子和空间环境的策略。

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Reversible Modulation of the Electronic and Spatial Environment around Ni(0) Centers Bearing Multifunctional Carbene Ligands with Triarylaluminum

Designing and modulating the electronic and spatial environments surrounding metal centers is a crucial issue in a wide range of chemistry fields that use organometallic compounds. Herein, we demonstrate a Lewis-acid-mediated reversible expansion, contraction, and transformation of the spatial environment surrounding nickel(0) centers that bear N-phosphine oxide-substituted N-heterocyclic carbenes (henceforth referred to as (S)PoxIms). Reaction between tetrahedral (syn-κ-C,O-(S)PoxIm)Ni(CO)₂ and Al(C₆F₅)₃ smoothly afforded heterobimetallic Ni/Al species such as trigonal-planar {κ-C-Ni(CO)₂}(μ-anti-(S)PoxIm){κ-O-Al(C₆F₅)₃} via a complexation-induced rotation of the N-phosphine oxide moieties, while the addition of 4-dimethylaminopyridine resulted in the quantitative regeneration of the former Ni complexes. The corresponding interconversion also occurred between (SPoxIm)Ni(η²:η²-diphenyldivinylsilane) and {κ-C-Ni(η²:η²-diene)}(μ-anti-SPoxIm){κ-O-Al(C₆F₅)₃} via the coordination and dissociation of Al(C₆F₅)₃. The shape and size of the space around the Ni(0) center was drastically changed through this Lewis-acid-mediated interconversion. Moreover, the multinuclear NMR, IR, and XAS analyses of the aforementioned carbonyl complexes clarified the details of the changes in the electronic states on the Ni centers; i.e., the electron delocalization was effectively enhanced among the Ni atom and CO ligands in the heterobimetallic Ni/Al species. The results presented in this work thus provide a strategy for reversibly modulating both the electronic and spatial environment of organometallic complexes, in addition to the well-accepted Lewis-base-mediated ligand-substitution methods.

更新日期：2023-07-19

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