Synthesis and Structural Elucidation of Triazolylmolybdenum(VI) Oxide Hybrids and Their Behavior as Oxidation Catalysts

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• 作者：Andrey B. Lysenko ; Ganna A. Senchyk ; Konstantin V. Domasevitch ; J眉rg Hauser ; Daniel Fuhrmann ; Merten Kobalz ; Harald Krautscheid ; Patr铆cia Neves ; Anabela A. Valente ; Isabel S. Gon莽alves
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：September 8, 2015
• 年：2015
• 卷：54
• 期：17
• 页码：8327-8338
• 全文大小：875K
• ISSN：1520-510X

文摘

A large family of bifunctional 1,2,4-triazole molecular tectons (tr) has been explored for engineering molybdenum(VI) oxide hybrid solids. Specifically, tr ligands bearing auxiliary basic or acidic groups were of the type amine, pyrazole, 1H-tetrazole, and 1,2,4-triazole. The organically templated molybdenum(VI) oxide solids with the general compositions [MoO₃(tr)], [Mo₂O₆(tr)], and [Mo₂O₆(tr)(H₂O)₂] were prepared under mild hydrothermal conditions or by refluxing in water. Their crystal structures consist of zigzag chains, ribbons, or helixes of alternating cis-{MoO₄N₂} or {MoO₅N} polyhedra stapled by short [N鈥揘]-tr bridges that for bitriazole ligands convert the motifs into 2D or 3D frameworks. The high thermal (235鈥?50 掳C) and chemical stability observed for the materials makes them promising for catalytic applications. The molybdenum(VI) oxide hybrids were successfully explored as versatile oxidation catalysts with tert-butyl hydroperoxide (TBHP) or aqueous H₂O₂ as an oxygen source, at 70 掳C. Catalytic performances were influenced by the different acidic鈥揵asic properties and steric hindrances of coordinating organic ligands as well as the structural dimensionality of the hybrid.