Taming the Oxidative Power of SeO3 in 1,4-Dioxane, Isolation of Two New Isomers of Mixed-Valence Selenium Oxides, and Two Unprecedented Cyclic Esters of Selenic Acid

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• 作者：Lukas Richtera ; Vojtech Jancik ; Diego Mart铆nez-Otero ; Ales Pokluda ; Zdirad Zak ; Jan Taraba ; Jiri Touzin
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：July 7, 2014
• 年：2014
• 卷：53
• 期：13
• 页码：6569-6577
• 全文大小：379K
• ISSN：1520-510X

文摘

The reaction of (SeO₃)₄ with 1,4-dioxane (diox, dioxane) with or without diluting solvent led to the isolation of the unprecedented esters of selenic acid-1,2-ethyl selenate (CH₂O)₂SeO₂ and the glyoxal diselenate O₂Se[(OCHO)₂]SeO₂. It was possible to isolate an unknown dimeric form of Se₂O₅ (Se₄O₁₀路(diox)₂) and a geometrical isomer of the mixed-valence oxide trans-Se₃O₇, both stabilized by dioxane. The dioxane adduct of monomeric selenium trioxide SeO₃路diox was obtained from the reaction of (SeO₃)₄ with dioxane in liquid SO₂. The reaction mechanism for the formation of these compounds was elucidated, and the molecular structure of the unstable form of the selenium trioxide was determined, consisting in a trimeric arrangement (SeO₃)₃.