Mechanism of Al3+-Catalyzed Oxidations of Hydrocarbons: Dramatic Activation of H2O2 toward O鈭扥 Homolysis in Complex [Al(H2O)4(OOH)(H2O

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• 作者：Maxim L. Kuznetsov ; Yuriy N. Kozlov ; Dalmo Mandelli ; Armando J. L. Pombeiro ; Georgiy B. Shul鈥檖in
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：May 2, 2011
• 年：2011
• 卷：50
• 期：9
• 页码：3996-4005
• 全文大小：1072K
• 年卷期：v.50,no.9(May 2, 2011)
• ISSN：1520-510X

文摘

A radical mechanism of hydrocarbon oxidations with the environmentally friendly and cheap homogeneous nontransition metal system [Al(Hb>2b>O)b>6b>]³⁺/Hb>2b>Ob>2b>/MeCN鈭扝b>2b>O was proposed for the first time on the basis of DFT calculations. A dramatic activation of Hb>2b>Ob>2b> toward homolysis in the key intermediate [Al(Hb>2b>O)b>4b>(OOH)(Hb>2b>Ob>2b>)]²⁺ due to the presence of the easily oxidizable OOH coligand provides, without a change of metal oxidation state, the generation of HO^{鈥?/sup> radicals, which then oxidize hydrocarbons. Nonradical mechanisms of the olefin epoxidation with the same catalytic system were also investigated.}