title: Mechanism of Oxygen Atom Transfer from Fe(V)(O) to Olefins at Room Temperature.
abstract: 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-TAML 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(-1) s(-1)) and electron-deficient (methyl trans-cinnamate; k2 = 0.03 M(-1) s(-1)) 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-C bond rotation to yield both stereoisomers of stilbene-epoxide. Additionally, a Hammett ρ 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.
authors.affiliation: †Chemical Engineering Division and ‡Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, CSIR-National Chemical Laboratory, Pune 411008, India.
authors.forename: Kundan K
authors.initials: KK
authors.lastname: Singh
authors.affiliation: †Chemical Engineering Division and ‡Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, CSIR-National Chemical Laboratory, Pune 411008, India.
authors.forename: Mrityunjay K
authors.initials: MK
authors.lastname: Tiwari
authors.affiliation: †Chemical Engineering Division and ‡Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, CSIR-National Chemical Laboratory, Pune 411008, India.
authors.forename: Basab B
authors.initials: BB
authors.lastname: Dhar
authors.affiliation: †Chemical Engineering Division and ‡Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, CSIR-National Chemical Laboratory, Pune 411008, India.
authors.forename: Kumar
authors.initials: K
authors.lastname: Vanka
authors.affiliation: †Chemical Engineering Division and ‡Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, CSIR-National Chemical Laboratory, Pune 411008, India.
authors.forename: Sayam
authors.initials: S
authors.lastname: Sen Gupta
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D005290:Ferric Compounds / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D013696:Temperature
chemical_list: D000475:Alkenes; D005290:Ferric Compounds; C000499:ferric oxide; D007501:Iron; D010100:Oxygen