Unveiling of a Trinuclear Cyclic Peroxidovanadate: A Potential Oxidant in Vanadium-Catalyzed Reactions

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• 作者：Luk谩拧 Krivosudsk媒 ; Peter Schwendt ; R贸bert Gyepes
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：July 6, 2015
• 年：2015
• 卷：54
• 期：13
• 页码：6306-6311
• 全文大小：363K
• ISSN：1520-510X

文摘

The first peroxidovanadium trimer was prepared in the form of its tetrabutylammonium salt, (NBu₄)₃[V₃O₃(O₂)₆]路2H₂O. Its X-ray structure analysis revealed a unique cyclic structure of the [V₃O₃(O₂)₆]^{3鈥?/sup> ion incorporating the yet unobserved 渭₃-畏2:畏1:畏1 coordination mode of one of its peroxido ligands. While relatively stable in nonaqueous solvents, the [V₃O₃(O₂)₆]3鈥?/sup> ion quickly decomposes in diluted aqueous solutions. A higher vanadium concentration or a higher CH₃CN content in the mixed CH₃CN/H₂O solvent facilitates the formation of oligomers [V₂O₂(O₂)₄(H₂O)]2鈥?/sup> and [V₃O₃(O₂)₆]3鈥?/sup>. 51V NMR investigations indicated that the trinuclear species is incorporated in vanadium-catalyzed oxidations in the presence of H₂O₂.}