Mechanism of Oxygen Atom Transfer from FeV(O) to Olefins at Room Temperature

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• 作者：Kundan K. Singh ; Mrityunjay k. Tiwari ; Basab B. Dhar ; Kumar Vanka ; Sayam Sen Gupta
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：July 6, 2015
• 年：2015
• 卷：54
• 期：13
• 页码：6112-6121
• 全文大小：634K
• ISSN：1520-510X

文摘

In biological oxidations, the intermediate Fe^V(O)(OH) has been proposed to be the active species for catalyzing the epoxidation of alkenes by nonheme iron complexes. However, no study has been reported yet that elucidates the mechanism of direct O-atom transfer during the reaction of Fe^V(O) with alkenes to form the corresponding epoxide. For the first time, we study the mechanism of O-atom transfer to alkenes using the Fe^V(O) complex of biuret-modified Fe鈥揟AML at room temperature. The second-order rate constant (k₂) for the reaction of different alkenes with Fe^V(O) was determined under single-turnover conditions. An 8000-fold rate difference was found between electron-rich (4-methoxystyrene; k₂ = 216 M^鈥? s^鈥?) and electron-deficient (methyl trans-cinnamate; k₂ = 0.03 M^鈥? s^鈥?) substrates. This rate difference indicates the electrophilic character of Fe^V(O). The use of cis-stilbene as a mechanistic probe leads to the formation of both cis- and trans-stilbene epoxides (73:27). This suggests the formation of a radical intermediate, which would allow C鈥揅 bond rotation to yield both stereoisomers of stilbene鈥揺poxide. Additionally, a Hammett 蟻 value of 鈭?.56 was obtained for the para-substituted styrene derivatives. Detailed DFT calculations show that the reaction proceeds via a two-step process through a doublet spin surface. Finally, using biuret-modified Fe鈥揟AML as the catalyst and NaOCl as the oxidant under catalytic conditions epoxide was formed with modest yields and turnover numbers.