Dramatically Accelerated Selective Oxygen-Atom Transfer by a Nonheme Iron(IV)-Oxo Complex: Tuning of the First and Second Coordination Spheres

[Image: see text] The new ligand N3Py(amide)SR and its Fe(II) complex [Fe(II)(N3Py(amide)SR)](BF(4))(2) (1) are described. Reaction of 1 with PhIO at −40 °C gives metastable [Fe(IV)(O)(N3Py(amide)SR)](2+) (2), containing a sulfide ligand and a single amide H-bond donor in proximity to the terminal o...

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Autores principales: Widger, Leland R., Davies, Casey G., Yang, Tzuhsiung, Siegler, Maxime A., Troeppner, Oliver, Jameson, Guy N. L., Ivanović-Burmazović, Ivana, Goldberg, David P.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4004223/
https://www.ncbi.nlm.nih.gov/pubmed/24471779
http://dx.doi.org/10.1021/ja410240c
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author Widger, Leland R.
Davies, Casey G.
Yang, Tzuhsiung
Siegler, Maxime A.
Troeppner, Oliver
Jameson, Guy N. L.
Ivanović-Burmazović, Ivana
Goldberg, David P.
author_facet Widger, Leland R.
Davies, Casey G.
Yang, Tzuhsiung
Siegler, Maxime A.
Troeppner, Oliver
Jameson, Guy N. L.
Ivanović-Burmazović, Ivana
Goldberg, David P.
author_sort Widger, Leland R.
collection PubMed
description [Image: see text] The new ligand N3Py(amide)SR and its Fe(II) complex [Fe(II)(N3Py(amide)SR)](BF(4))(2) (1) are described. Reaction of 1 with PhIO at −40 °C gives metastable [Fe(IV)(O)(N3Py(amide)SR)](2+) (2), containing a sulfide ligand and a single amide H-bond donor in proximity to the terminal oxo group. Direct evidence for H-bonding is seen in a structural analogue, [Fe(II)(Cl)(N3Py(amide)SR)](BF(4))(2) (3). Complex 2 exhibits rapid O-atom transfer (OAT) toward external sulfide substrates, but no intramolecular OAT. However, direct S-oxygenation does occur in the reaction of 1 with mCPBA, yielding sulfoxide-ligated [Fe(II)(N3Py(amide)S(O)R)](BF(4))(2) (4). Catalytic OAT with 1 was also observed.
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spelling pubmed-40042232015-01-28 Dramatically Accelerated Selective Oxygen-Atom Transfer by a Nonheme Iron(IV)-Oxo Complex: Tuning of the First and Second Coordination Spheres Widger, Leland R. Davies, Casey G. Yang, Tzuhsiung Siegler, Maxime A. Troeppner, Oliver Jameson, Guy N. L. Ivanović-Burmazović, Ivana Goldberg, David P. J Am Chem Soc [Image: see text] The new ligand N3Py(amide)SR and its Fe(II) complex [Fe(II)(N3Py(amide)SR)](BF(4))(2) (1) are described. Reaction of 1 with PhIO at −40 °C gives metastable [Fe(IV)(O)(N3Py(amide)SR)](2+) (2), containing a sulfide ligand and a single amide H-bond donor in proximity to the terminal oxo group. Direct evidence for H-bonding is seen in a structural analogue, [Fe(II)(Cl)(N3Py(amide)SR)](BF(4))(2) (3). Complex 2 exhibits rapid O-atom transfer (OAT) toward external sulfide substrates, but no intramolecular OAT. However, direct S-oxygenation does occur in the reaction of 1 with mCPBA, yielding sulfoxide-ligated [Fe(II)(N3Py(amide)S(O)R)](BF(4))(2) (4). Catalytic OAT with 1 was also observed. American Chemical Society 2014-01-28 2014-02-19 /pmc/articles/PMC4004223/ /pubmed/24471779 http://dx.doi.org/10.1021/ja410240c Text en Copyright © 2014 American Chemical Society
spellingShingle Widger, Leland R.
Davies, Casey G.
Yang, Tzuhsiung
Siegler, Maxime A.
Troeppner, Oliver
Jameson, Guy N. L.
Ivanović-Burmazović, Ivana
Goldberg, David P.
Dramatically Accelerated Selective Oxygen-Atom Transfer by a Nonheme Iron(IV)-Oxo Complex: Tuning of the First and Second Coordination Spheres
title Dramatically Accelerated Selective Oxygen-Atom Transfer by a Nonheme Iron(IV)-Oxo Complex: Tuning of the First and Second Coordination Spheres
title_full Dramatically Accelerated Selective Oxygen-Atom Transfer by a Nonheme Iron(IV)-Oxo Complex: Tuning of the First and Second Coordination Spheres
title_fullStr Dramatically Accelerated Selective Oxygen-Atom Transfer by a Nonheme Iron(IV)-Oxo Complex: Tuning of the First and Second Coordination Spheres
title_full_unstemmed Dramatically Accelerated Selective Oxygen-Atom Transfer by a Nonheme Iron(IV)-Oxo Complex: Tuning of the First and Second Coordination Spheres
title_short Dramatically Accelerated Selective Oxygen-Atom Transfer by a Nonheme Iron(IV)-Oxo Complex: Tuning of the First and Second Coordination Spheres
title_sort dramatically accelerated selective oxygen-atom transfer by a nonheme iron(iv)-oxo complex: tuning of the first and second coordination spheres
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4004223/
https://www.ncbi.nlm.nih.gov/pubmed/24471779
http://dx.doi.org/10.1021/ja410240c
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