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

Yoon Hye Kwon; Binh Khanh Mai; Yong Min Lee; Sunder N. Dhuri; Debasish Mandal; Kyung Bin Cho; Yongho Kim; Sason Shaik; Wonwoo Nam

doi:10.1021/acs.jpclett.5b00527

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

Yoon Hye Kwon, Binh Khanh Mai, Yong Min Lee, Sunder N. Dhuri, Debasish Mandal, Kyung Bin Cho, Yongho Kim, Sason Shaik, Wonwoo Nam

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

61 Scopus citations

Abstract

We show by experiments that nonheme Fe^IVO 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 Fe^IVO species. By modeling the 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 a SIP value by combining experimental and theoretical results.

Original language	English
Pages (from-to)	1472-1476
Number of pages	5
Journal	Journal of Physical Chemistry Letters
Volume	6
Issue number	8
DOIs	https://doi.org/10.1021/acs.jpclett.5b00527
State	Published - 16 Apr 2015

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

Keywords

density functional theory
kinetic isotope effect
spin inversion
tunneling
two-state reactivity

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10.1021/acs.jpclett.5b00527

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

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 the 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 a SIP value by combining experimental and theoretical results.",

keywords = "density functional theory, kinetic isotope effect, spin inversion, tunneling, two-state reactivity",

author = "Kwon, {Yoon Hye} and Mai, {Binh Khanh} and Lee, {Yong Min} and Dhuri, {Sunder N.} and Debasish Mandal and Cho, {Kyung Bin} and Yongho Kim and Sason Shaik and Wonwoo Nam",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2015",

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day = "16",

doi = "10.1021/acs.jpclett.5b00527",

language = "English",

volume = "6",

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journal = "Journal of Physical Chemistry Letters",

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TY - JOUR

T1 - Determination of spin inversion probability, H-tunneling correction, and regioselectivity in the two-state reactivity of nonheme iron(IV)-oxo complexes

AU - Kwon, Yoon Hye

AU - Mai, Binh Khanh

AU - Lee, Yong Min

AU - Dhuri, Sunder N.

AU - Mandal, Debasish

AU - Cho, Kyung Bin

AU - Kim, Yongho

AU - Shaik, Sason

AU - Nam, Wonwoo

PY - 2015/4/16

Y1 - 2015/4/16

N2 - 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 the 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 a SIP value by combining experimental and theoretical results.

AB - 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 the 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 a SIP value by combining experimental and theoretical results.

KW - density functional theory

KW - kinetic isotope effect

KW - spin inversion

KW - tunneling

KW - two-state reactivity

UR - http://www.scopus.com/inward/record.url?scp=84927939008&partnerID=8YFLogxK

U2 - 10.1021/acs.jpclett.5b00527

DO - 10.1021/acs.jpclett.5b00527

M3 - Article

AN - SCOPUS:84927939008

SN - 1948-7185

VL - 6

SP - 1472

EP - 1476

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

IS - 8

ER -

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

Abstract

Bibliographical note

Keywords

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