02238nas a2200193   4500008004100000022001400041245008200055210006900137260007100206300001400277490000700291520153500298100002201833700002701855700002001882700001701902700002201919856010301941       2015                        eng d  a0020-166900aMechanism of oxygen atom transfer from Fe-V(O) to olefins at room temperature0 aMechanism of oxygen atom transfer from FeVO to olefins at room t  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUL  a6112-61210 v543 a<p>In biological oxidations, the intermediate Fe-V(0)(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(0) 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(0) complex of biuret-modified Fe-TAML at room temperature. The second-order rate constant (k(2)) for the reaction of different alkenes with Fe-V(0) was determined under single-turnover conditions. An 8000-fold rate difference was found between electron-rich (4-methoxystyrene; k(2) = 216 M-1 s(-1)) and electron-deficient (methyl transcinnamate; k(2) = 0.03 M-1 s(-1)) substrates. This rate difference indicates the electrophilic character of Fe-V(0). 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-C bond rotation to yield both stereoisomers of stilbene-epoxide. Additionally, a Hammett rho value of -0.56 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-TAML as the catalyst and NaOCl as the oxidant under catalytic conditions epoxide was formed with modest yields and turnover numbers.</p>1 aSingh, Kundan, K.1 aTiwari, Mrityunjay, K.1 aDhar, Basab, B.1 aVanka, Kumar1 aGupta, Sayam, Sen  uhttps://library.ncl.res.in/content/mechanism-oxygen-atom-transfer-fe-vo-olefins-room-temperature-0