Determination of spin inversion probability, H-tunneling correction and regioselectivity in the two-state reactivity of nonheme iron(IV)-oxo complexes

Kwon, Y.H.; Mai, B.K.; Lee, Y-M.; Dhuri, S.N.; Mandal, D.; Cho, K-B.; Kim, Y.; Shaik, S.; Nam, W.

dc.contributor.author	Kwon, Y.H.
dc.contributor.author	Mai, B.K.
dc.contributor.author	Lee, Y-M.
dc.contributor.author	Dhuri, S.N.
dc.contributor.author	Mandal, D.
dc.contributor.author	Cho, K-B.
dc.contributor.author	Kim, Y.
dc.contributor.author	Shaik, S.
dc.contributor.author	Nam, W.
dc.date.accessioned	2015-09-29T06:43:28Z
dc.date.available	2015-09-29T06:43:28Z
dc.date.issued	2015
dc.identifier.citation	Journal of Physical Chemistry Letters. 6(8); 2015; 1472-1476.	en_US
dc.identifier.uri	http://dx.doi.org/10.1021/acs.jpclett.5b00527
dc.identifier.uri	http://irgu.unigoa.ac.in/drs/handle/unigoa/4019
dc.description.abstract	We show by experiments that nonheme FeIVO species react with cyclohexene to yield selective hydrogen atom transfer (HAT) reactions with virtually no C=C epoxidation. Straightforward DFT calculations reveal, however, that C=C epoxidation on the S = 2 state possesses a low energy barrier and should contribute substantially to the oxidation of cyclohexene by the nonheme FeIVO species. By modeling selectivity of this two-site reactivity, we show that an interplay of tunneling and spin inversion probability (SIP) reverses the apparent barriers and prefers exclusive S = 1 HAT over mixed HAT and C=C epoxidation on S = 2. The model enables us to derive an SIP value by combining experimental and theoretical results.	en_US
dc.subject	Chemistry	en_US
dc.title	Determination of spin inversion probability, H-tunneling correction and regioselectivity in the two-state reactivity of nonheme iron(IV)-oxo complexes	en_US
dc.type	Journal article	en_US
dc.identifier.impf	y