@article { ISI:000367118100023,
	title = {Mechanism of alcohol oxidation by Fe-V(O) at room temperature},
	journal = {Inorganic Chemistry},
	volume = {54},
	number = {24},
	year = {2015},
	month = {DEC},
	pages = {11792-11798},
	publisher = {AMER CHEMICAL SOC},
	address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA},
	abstract = {<p>{Selective oxidation of alcohol to its corresponding carbonyl compound is an important chemical process in biological as well as industrial reactions, The heme containing enzyme CytP450 has been known to selectively oxidize akohols to their corresponding carbonyl compounds. The mechanism of this reaction, which involves high-valent Fe-IV(O)-porphyrin(center dot+) intermediate with alcohol, has been well-studied extensively both with the native enzyme and with model complexes. In this paper, we report for the first time the mechanistic insight of, alcohol oxidation with Fe-V(O) complex of biuret TAML (bTAML), Which is isoelectronic with Fe-IV(O)-porphyrin(center dot+) intermediate form in CytP450. The oxidations displayed saturation kinetics, which allowed us to determine both the binding constants and first-order rate constants for the reaction. The K and k values observed for thel oxidation of benzyl alcohol by Fe-V(O) at room temperature (K = 300 M-1</p>},
	issn = {0020-1669},
	doi = {10.1021/acs.inorgchem.5b01937},
	author = {Ghosh, Munmun and Nikhil, Y. L. K. and Dhar, Basab B. and Sen Gupta, Sayam}
}
@article { ISI:000357705800012,
	title = {Mechanism of oxygen atom transfer from Fe-V(O) to olefins at room temperature},
	journal = {Inorganic Chemistry},
	volume = {54},
	number = {13},
	year = {2015},
	month = {JUL},
	pages = {6112-6121},
	publisher = {AMER CHEMICAL SOC},
	address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA},
	abstract = {<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>},
	issn = {0020-1669},
	doi = {10.1021/ic503053q},
	author = {Singh, Kundan K. and Tiwari, Mrityunjay K. and Dhar, Basab B. and Vanka, Kumar and Sen Gupta, Sayam}
}
