1H-ENDOR evidence for a hydrogen-bonding interaction that modulates the reactivity of a nonheme FeIV=O unit

Muralidharan Shanmugam; Genqiang Xue; Lawrence Que; Brian M. Hoffman

doi:10.1021/ic3015783

¹H-ENDOR evidence for a hydrogen-bonding interaction that modulates the reactivity of a nonheme Fe^IV=O unit

Muralidharan Shanmugam
, Genqiang Xue
, Lawrence Que
, Brian M. Hoffman

Chemistry (Twin Cities)

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

10 Scopus citations

Abstract

We report that a novel use of 35 GHz ¹H-ENDOR spectroscopy establishes the presence in 1 of an Fe^IV-O⋯H-O-Fe ^III hydrogen bond predicted by density functional theory computations to generate a six-membered-ring core for 1. The hydrogen bond rationalizes the difference in the C-H bond cleavage reactivity between 1 and 4 (OCH₃) (where a CH₃O group has replaced the HO on the Fe^III site). This result substantiates the seemingly paradoxical conclusion that the nonheme Fe^IV-O unit of 1 not only has the electrophilic character required for H-atom abstraction but also retains sufficient nucleophilic character to accept a hydrogen bond from the Fe^III-OH unit.

Original language	English (US)
Pages (from-to)	10080-10082
Number of pages	3
Journal	Inorganic chemistry
Volume	51
Issue number	19
DOIs	https://doi.org/10.1021/ic3015783
State	Published - Oct 1 2012

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abstract = "We report that a novel use of 35 GHz 1H-ENDOR spectroscopy establishes the presence in 1 of an FeIV-O⋯H-O-Fe III hydrogen bond predicted by density functional theory computations to generate a six-membered-ring core for 1. The hydrogen bond rationalizes the difference in the C-H bond cleavage reactivity between 1 and 4 (OCH3) (where a CH3O group has replaced the HO on the FeIII site). This result substantiates the seemingly paradoxical conclusion that the nonheme FeIV-O unit of 1 not only has the electrophilic character required for H-atom abstraction but also retains sufficient nucleophilic character to accept a hydrogen bond from the FeIII-OH unit.",

author = "Muralidharan Shanmugam and Genqiang Xue and Lawrence Que and Hoffman, \{Brian M.\}",

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T1 - 1H-ENDOR evidence for a hydrogen-bonding interaction that modulates the reactivity of a nonheme FeIV=O unit

AU - Shanmugam, Muralidharan

AU - Xue, Genqiang

AU - Que, Lawrence

AU - Hoffman, Brian M.

PY - 2012/10/1

Y1 - 2012/10/1

N2 - We report that a novel use of 35 GHz 1H-ENDOR spectroscopy establishes the presence in 1 of an FeIV-O⋯H-O-Fe III hydrogen bond predicted by density functional theory computations to generate a six-membered-ring core for 1. The hydrogen bond rationalizes the difference in the C-H bond cleavage reactivity between 1 and 4 (OCH3) (where a CH3O group has replaced the HO on the FeIII site). This result substantiates the seemingly paradoxical conclusion that the nonheme FeIV-O unit of 1 not only has the electrophilic character required for H-atom abstraction but also retains sufficient nucleophilic character to accept a hydrogen bond from the FeIII-OH unit.

AB - We report that a novel use of 35 GHz 1H-ENDOR spectroscopy establishes the presence in 1 of an FeIV-O⋯H-O-Fe III hydrogen bond predicted by density functional theory computations to generate a six-membered-ring core for 1. The hydrogen bond rationalizes the difference in the C-H bond cleavage reactivity between 1 and 4 (OCH3) (where a CH3O group has replaced the HO on the FeIII site). This result substantiates the seemingly paradoxical conclusion that the nonheme FeIV-O unit of 1 not only has the electrophilic character required for H-atom abstraction but also retains sufficient nucleophilic character to accept a hydrogen bond from the FeIII-OH unit.

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JO - Inorganic chemistry

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IS - 19

ER -

¹H-ENDOR evidence for a hydrogen-bonding interaction that modulates the reactivity of a nonheme Fe^IV=O unit

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