Secondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach

[Image: see text] The new biomimetic ligands N4Py(2Ph) (1) and N4Py(2Ph,amide) (2) were synthesized and yield the iron(II) complexes [Fe(II)(N4Py(2Ph))(NCCH(3))](BF(4))(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...

Descripción completa

Detalles Bibliográficos
Autores principales: Sahu, Sumit, Widger, Leland R., Quesne, Matthew G., de Visser, Sam P., Matsumura, Hirotoshi, Moënne-Loccoz, Pierre, Siegler, Maxime A., Goldberg, David P.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2013
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3746373/
https://www.ncbi.nlm.nih.gov/pubmed/23834409
http://dx.doi.org/10.1021/ja402688t
_version_ 1782280818699272192
author Sahu, Sumit
Widger, Leland R.
Quesne, Matthew G.
de Visser, Sam P.
Matsumura, Hirotoshi
Moënne-Loccoz, Pierre
Siegler, Maxime A.
Goldberg, David P.
author_facet Sahu, Sumit
Widger, Leland R.
Quesne, Matthew G.
de Visser, Sam P.
Matsumura, Hirotoshi
Moënne-Loccoz, Pierre
Siegler, Maxime A.
Goldberg, David P.
author_sort Sahu, Sumit
collection PubMed
description [Image: see text] The new biomimetic ligands N4Py(2Ph) (1) and N4Py(2Ph,amide) (2) were synthesized and yield the iron(II) complexes [Fe(II)(N4Py(2Ph))(NCCH(3))](BF(4))(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(III)OOR species which decays without arene hydroxylation. These results provide new insights regarding the impact of secondary coordination sphere effects at nonheme iron centers.
format Online
Article
Text
id pubmed-3746373
institution National Center for Biotechnology Information
language English
publishDate 2013
publisher American Chemical Society
record_format MEDLINE/PubMed
spelling pubmed-37463732013-08-19 Secondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach Sahu, Sumit Widger, Leland R. Quesne, Matthew G. de Visser, Sam P. Matsumura, Hirotoshi Moënne-Loccoz, Pierre Siegler, Maxime A. Goldberg, David P. J Am Chem Soc [Image: see text] The new biomimetic ligands N4Py(2Ph) (1) and N4Py(2Ph,amide) (2) were synthesized and yield the iron(II) complexes [Fe(II)(N4Py(2Ph))(NCCH(3))](BF(4))(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(III)OOR species which decays without arene hydroxylation. These results provide new insights regarding the impact of secondary coordination sphere effects at nonheme iron centers. American Chemical Society 2013-07-08 2013-07-24 /pmc/articles/PMC3746373/ /pubmed/23834409 http://dx.doi.org/10.1021/ja402688t Text en Copyright © 2013 American Chemical Society Terms of Use CC-BY (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html)
spellingShingle Sahu, Sumit
Widger, Leland R.
Quesne, Matthew G.
de Visser, Sam P.
Matsumura, Hirotoshi
Moënne-Loccoz, Pierre
Siegler, Maxime A.
Goldberg, David P.
Secondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach
title Secondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach
title_full Secondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach
title_fullStr Secondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach
title_full_unstemmed Secondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach
title_short Secondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach
title_sort secondary coordination sphere influence on the reactivity of nonheme iron(ii) complexes: an experimental and dft approach
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3746373/
https://www.ncbi.nlm.nih.gov/pubmed/23834409
http://dx.doi.org/10.1021/ja402688t
work_keys_str_mv AT sahusumit secondarycoordinationsphereinfluenceonthereactivityofnonhemeironiicomplexesanexperimentalanddftapproach
AT widgerlelandr secondarycoordinationsphereinfluenceonthereactivityofnonhemeironiicomplexesanexperimentalanddftapproach
AT quesnematthewg secondarycoordinationsphereinfluenceonthereactivityofnonhemeironiicomplexesanexperimentalanddftapproach
AT devissersamp secondarycoordinationsphereinfluenceonthereactivityofnonhemeironiicomplexesanexperimentalanddftapproach
AT matsumurahirotoshi secondarycoordinationsphereinfluenceonthereactivityofnonhemeironiicomplexesanexperimentalanddftapproach
AT moenneloccozpierre secondarycoordinationsphereinfluenceonthereactivityofnonhemeironiicomplexesanexperimentalanddftapproach
AT sieglermaximea secondarycoordinationsphereinfluenceonthereactivityofnonhemeironiicomplexesanexperimentalanddftapproach
AT goldbergdavidp secondarycoordinationsphereinfluenceonthereactivityofnonhemeironiicomplexesanexperimentalanddftapproach

Ejemplares similares