Stabilization of Ni(I)(1,4,8,11‐tetraazacyclotetradecane)+ in a Sol‐Gel Matrix: It's Plausible Use in Catalytic Processes,Israel Journal of Chemistry

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Stabilization of Ni(I)(1,4,8,11‐tetraazacyclotetradecane)+ in a Sol‐Gel Matrix: It's Plausible Use in Catalytic Processes
Israel Journal of Chemistry ( IF 2.3 ) Pub Date : 2020-01-16 , DOI: 10.1002/ijch.201900139
Dror Shamir ₁ , Yaniv Wolfer ₂ , Alexander I. Shames ₃ , Yael Albo ₄ , Ariela Burg ₅

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Monovalent nickel is used as a catalyst in a diversity of important chemical systems due to its properties as a strong reducing agent. However, monovalent nickel is unstable in homogeneous systems; its lifetime is very short, and therefore, its efficiency as a catalyst is quite limited. In this article, we demonstrate the catalytic capabilities of Ni(I)(1,4,8,11‐tetraazacyclotetradecane)⁺ as a reducing and catalytic agent by its entrapment in the silica sol gel matrix. The EPR results indicate that the sol‐gel matrix plays two roles: it inhibits the common mechanism of Ni(I)L⁺ decomposition in aqueous solutions, and it also facilitates its functionality as a heterogeneous catalyst, by stabilizing it for at least several hours. The activity of Ni(I)L⁺ which is entrapped within the matrix, was studied by reducing 2,2‐Bis(bromomethyl)‐1,3‐Propanediol and I₃⁻. The results indicate that Ni(I)L⁺/Ni(III)L−H²⁺ acts as a good reducing agent. These results have important implications for a variety of essential catalytic reactions by shedding light on a new feature of sol‐gel matrices and their use as active species stabilizers.

中文翻译：

溶胶-凝胶基质中Ni（I）（1,4,8,11-四氮杂环十四烷）+的稳定化：在催化过程中可能有用

一价镍由于其作为强还原剂的性质而在多种重要的化学体系中用作催化剂。但是，一价镍在均相系统中不稳定。它的寿命很短，因此，它作为催化剂的效率非常有限。在本文中，我们通过将Ni（I）（1,4,8,11-四氮杂环十四烷）⁺截留在硅胶溶胶凝胶基质中来证明其作为还原剂和催化剂的催化能力。EPR结果表明，溶胶-凝胶基体起着两个作用：抑制水溶液中Ni（I）L ⁺分解的共同机理，并通过稳定至少几小时来促进其作为非均相催化剂的功能。Ni（I）L ⁺的活性其在基质内包埋，通过减少2,2-双（溴甲基）研究-1,3-丙二醇和我₃^-。结果表明，Ni（I）L ⁺ / Ni（III）L-H ^2+可作为良好的还原剂。这些结果通过阐明溶胶凝胶基质的新功能及其作为活性物质稳定剂的用途，对各种基本的催化反应具有重要意义。

更新日期：2020-01-16

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