Immobilization of Volatile and Corrosive Iodine Monochloride (ICl) and I2 Reagents in a Stable Metal鈥揙rganic Framework

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• 作者：Jun He ; Jingjing Duan ; Huatian Shi ; Jian Huang ; Jiahong Huang ; Lin Yu ; Matthias Zeller ; Allen D. Hunter ; Zhengtao Xu
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：July 7, 2014
• 年：2014
• 卷：53
• 期：13
• 页码：6837-6843
• 全文大小：346K
• ISSN：1520-510X

文摘

The major discovery here is a robust and water-stable metal鈥搊rganic framework (MOF) material capable of reversible binding of the volatile and reactive molecules of ICl and I₂. The immobilization of I₂ and ICl, as well as their controllable release thus achieved, is to facilitate the wide-ranging applications of these volatile species as catalysts and reagents in chemical and industrial processes. The framework material TMBP路CuI (hereafter TCuI) can be conveniently prepared in quantitative yields by heating CuI and the organic linker TMBP (3,3鈥?5,5鈥?tetramethyl-4,4鈥?bipyrazol) in acetonitrile. The microporous three-dimensional net of TCuI features CuI chains that contribute to efficient and reversible binding of ICl and I₂ molecules, to result in the stoichiometrically well-defined adducts of TCuI路ICl and TCuI路I₂, respectively. Moreover, the confinement of a volatile compound like ICl within the MOF medium provides unique opportunities to enhance its reactivity and selectivity as a chemical reagent, as is exemplified by the iodination reactions examined herein. With this exemplary study, we intend to stimulate interest in further exploring MOFs and other porous media (e.g., porous polymers) for entrapping ICl and other volatile reagents (e.g., Br₂, SCl₂, S₂Cl₂, and SOCl₂) and for potentially novel reactivity associated with the porous medium.