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

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

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. © 2013 American Chemical Society.

Original language	English
Pages (from-to)	10590-10593
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	135
Issue number	29
DOIs	https://doi.org/10.1021/ja402688t
Publication status	Published - 24 Jul 2013

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CCDC 955341: Experimental Crystal Structure Determination
Sahu, S. (Contributor), Widger, L. R. (Contributor), Quesne, M. (Contributor), De Visser, S. (Contributor), Matsumura, H. (Contributor), Moënne-Loccoz, P. (Contributor), Siegler, M. A. (Contributor) & Goldberg, D. P. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2013
DOI: 10.5517/cc1123gp, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc1123gp&sid=DataCite
Dataset
CCDC 955340: Experimental Crystal Structure Determination
Sahu, S. (Contributor), Widger, L. R. (Contributor), Quesne, M. (Contributor), De Visser, S. (Contributor), Matsumura, H. (Contributor), Moënne-Loccoz, P. (Contributor), Siegler, M. A. (Contributor) & Goldberg, D. P. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2013
DOI: 10.5517/cc1123fn, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc1123fn&sid=DataCite
Dataset
CCDC 955342: Experimental Crystal Structure Determination
Sahu, S. (Contributor), Widger, L. R. (Contributor), Quesne, M. (Contributor), De Visser, S. (Contributor), Matsumura, H. (Contributor), Moënne-Loccoz, P. (Contributor), Siegler, M. A. (Contributor) & Goldberg, D. P. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2013
DOI: 10.5517/cc1123hq, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc1123hq&sid=DataCite
Dataset

Cite this

@article{7b2cdd9198cc457d96145bb52bdc1779,

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. {\textcopyright} 2013 American Chemical Society.",

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.}",

note = "cited By 12",

year = "2013",

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day = "24",

doi = "10.1021/ja402688t",

language = "English",

volume = "135",

pages = "10590--10593",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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TY - JOUR

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

N1 - cited By 12

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. © 2013 American Chemical Society.

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. © 2013 American Chemical Society.

U2 - 10.1021/ja402688t

DO - 10.1021/ja402688t

M3 - Article

SN - 0002-7863

VL - 135

SP - 10590

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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Datasets

CCDC 955341: Experimental Crystal Structure Determination

CCDC 955340: Experimental Crystal Structure Determination

CCDC 955342: Experimental Crystal Structure Determination

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