Secondary coordination sphere influence on the reactivity of nonheme iron(II) complexes: An experimental and DFT approach

Sumit Sahu; Leland R. Widger; Matthew G. Quesne; Sam P. De Visser; Hirotoshi Matsumura; Pierre Moënne-Loccoz; Maxime A. Siegler; David P. Goldberg

doi:10.1021/ja402688t

Secondary coordination sphere influence on the reactivity of nonheme iron(II) complexes: An experimental and DFT approach

Sumit Sahu, Leland R. Widger, Matthew G. Quesne, Sam P. De Visser, Hirotoshi Matsumura, Pierre Moënne-Loccoz, Maxime A. Siegler, David P. Goldberg

Chemical Physiology and Biochemistry

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

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Abstract

The new biomimetic ligands N4Py^2Ph (1) and N4Py ^2Ph,amide (2) were synthesized and yield the iron(II) complexes [Fe^II(N4Py^2Ph)(NCCH₃)](BF₄) ₂ (3) and [Fe^II(N4Py^2Ph,amide)](BF ₄)₂ (5). Controlled orientation of the Ph substituents in 3 leads to facile triplet spin reactivity for a putative Fe^IV(O) intermediate, resulting in rapid arene hydroxylation. Addition of a peripheral amide substituent within hydrogen-bond distance of the iron first coordination sphere leads to stabilization of a high-spin Fe^IIIOOR species which decays without arene hydroxylation. These results provide new insights regarding the impact of secondary coordination sphere effects at nonheme iron centers.

Original language	English (US)
Pages (from-to)	10590-10593
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	135
Issue number	29
DOIs	https://doi.org/10.1021/ja402688t
State	Published - Jul 24 2013

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Secondary coordination sphere influence on the reactivity of nonheme iron(II) complexes: An experimental and DFT approach",

abstract = "The new biomimetic ligands N4Py2Ph (1) and N4Py 2Ph,amide (2) were synthesized and yield the iron(II) complexes [FeII(N4Py2Ph)(NCCH3)](BF4) 2 (3) and [FeII(N4Py2Ph,amide)](BF 4)2 (5). Controlled orientation of the Ph substituents in 3 leads to facile triplet spin reactivity for a putative FeIV(O) intermediate, resulting in rapid arene hydroxylation. Addition of a peripheral amide substituent within hydrogen-bond distance of the iron first coordination sphere leads to stabilization of a high-spin FeIIIOOR species which decays without arene hydroxylation. These results provide new insights regarding the impact of secondary coordination sphere effects at nonheme iron centers.",

author = "Sumit Sahu and Widger, {Leland R.} and Quesne, {Matthew G.} and {De Visser}, {Sam P.} and Hirotoshi Matsumura and Pierre Mo{\"e}nne-Loccoz and Siegler, {Maxime A.} and Goldberg, {David P.}",

year = "2013",

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doi = "10.1021/ja402688t",

language = "English (US)",

volume = "135",

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journal = "Journal of the American Chemical Society",

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TY - JOUR

T1 - Secondary coordination sphere influence on the reactivity of nonheme iron(II) complexes

T2 - An experimental and DFT approach

AU - Sahu, Sumit

AU - Widger, Leland R.

AU - Quesne, Matthew G.

AU - De Visser, Sam P.

AU - Matsumura, Hirotoshi

AU - Moënne-Loccoz, Pierre

AU - Siegler, Maxime A.

AU - Goldberg, David P.

PY - 2013/7/24

Y1 - 2013/7/24

N2 - The new biomimetic ligands N4Py2Ph (1) and N4Py 2Ph,amide (2) were synthesized and yield the iron(II) complexes [FeII(N4Py2Ph)(NCCH3)](BF4) 2 (3) and [FeII(N4Py2Ph,amide)](BF 4)2 (5). Controlled orientation of the Ph substituents in 3 leads to facile triplet spin reactivity for a putative FeIV(O) intermediate, resulting in rapid arene hydroxylation. Addition of a peripheral amide substituent within hydrogen-bond distance of the iron first coordination sphere leads to stabilization of a high-spin FeIIIOOR species which decays without arene hydroxylation. These results provide new insights regarding the impact of secondary coordination sphere effects at nonheme iron centers.

AB - The new biomimetic ligands N4Py2Ph (1) and N4Py 2Ph,amide (2) were synthesized and yield the iron(II) complexes [FeII(N4Py2Ph)(NCCH3)](BF4) 2 (3) and [FeII(N4Py2Ph,amide)](BF 4)2 (5). Controlled orientation of the Ph substituents in 3 leads to facile triplet spin reactivity for a putative FeIV(O) intermediate, resulting in rapid arene hydroxylation. Addition of a peripheral amide substituent within hydrogen-bond distance of the iron first coordination sphere leads to stabilization of a high-spin FeIIIOOR species which decays without arene hydroxylation. These results provide new insights regarding the impact of secondary coordination sphere effects at nonheme iron centers.

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DO - 10.1021/ja402688t

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SN - 0002-7863

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EP - 10593

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 29

ER -

Secondary coordination sphere influence on the reactivity of nonheme iron(II) complexes: An experimental and DFT approach

Abstract

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