View in EDS

One-electron oxidation of an oxoiron(IV) complex to form an [0=Fev=NR]+ center.

Saved in:
Bibliographic Details
Title: One-electron oxidation of an oxoiron(IV) complex to form an [0=Fev=NR]+ center.
Authors: Van Heuvelen, Katherine M.1,2, Fiedler, Adam T.1,2,3, Shan, Xiaopeng1,2, De Hont, Raymond F.4, Meier, Katlyn K.4, Bominaar, Emile L.4 eb7g@andrew.cmu.edu, Münck, Eckard4 emunck@cmu.edu, Que Jr., Lawrence1,2 larryque@umn.edu
Source: Proceedings of the National Academy of Sciences of the United States of America. 7/24/2012, Vol. 109 Issue 30, p11933-11938. 6p.
Subjects: Electrons, Oxidation, Iron catalysts, Dioxygenases, Metal complexes, Bioinorganic chemistry
Abstract: Oxoiron(V) species are postulated to be involved in the mechanisms of the arene cis-dihydroxylating Rieske dioxygenases and of bioinspired nonheme iron catalysts for alkane hydroxylation, olefin cis-dihydroxylation, and water oxidation. In an effort to obtain a synthetic oxoiron(V) complex, we report herein the oneelectron oxidation of the S = 1 complex [FeIv(0)(TMC)(NCCH3)]2+ (1, where TMC is tetramethylcyclam) by treatment with tert -butyl hydroperoxide and strong base in acetonitrile to generate a metastable s = 1/2 complex 2 at -44°C, which has been characterized by UV-visible, resonance Raman, Mössbauer, and EPR methods. The defining spectroscopic characteristic of 2 is the unusual x / y anisotropy observed for the 57Fe and 170 A tensors associated with the high-valent Fe=0 unit and for the 14N A tensor of a ligand derived from acetonitrile. As shown by detailed density functional theory (DFT) calculations, the unusual x / y anisotropy observed can only arise from an iron center with substantially different spin populations in the dxz and dyz orbitals, which cannot correspond to an FeIV=0 unit but is fully consistent with an s = 1/2 Fev center, like that found for [Fev(0)(TAML)]- (where TAML is tetraamido macrocyclic ligand), the only well-characterized oxoiron(V) complex reported. Mass spectral analysis shows that the generation of 2 entails the addition of an oxygen atom to 1 and the loss of one positive charge. Taken together, the spectroscopic data and DFT calculations support the formulation of 2 as an iron(V) complex having axial oxo and acetylimido ligands, namely [Fev(0)(TMC)(NC(0)CH3)]+. [ABSTRACT FROM AUTHOR]
Copyright of Proceedings of the National Academy of Sciences of the United States of America is the property of National Academy of Sciences and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
FullText Text:
  Availability: 0
Header DbId: egs
DbLabel: Engineering Source
An: 78276697
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
IllustrationInfo
Items – Name: Title
  Label: Title
  Group: Ti
  Data: One-electron oxidation of an oxoiron(IV) complex to form an [0=Fe<superscript>v</superscript>=NR]<superscript>+</superscript> center.
– Name: Author
  Label: Authors
  Group: Au
  Data: <searchLink fieldCode="AR" term="%22Van+Heuvelen%2C+Katherine+M%2E%22">Van Heuvelen, Katherine M.</searchLink><relatesTo>1,2</relatesTo><br /><searchLink fieldCode="AR" term="%22Fiedler%2C+Adam+T%2E%22">Fiedler, Adam T.</searchLink><relatesTo>1,2,3</relatesTo><br /><searchLink fieldCode="AR" term="%22Shan%2C+Xiaopeng%22">Shan, Xiaopeng</searchLink><relatesTo>1,2</relatesTo><br /><searchLink fieldCode="AR" term="%22De+Hont%2C+Raymond+F%2E%22">De Hont, Raymond F.</searchLink><relatesTo>4</relatesTo><br /><searchLink fieldCode="AR" term="%22Meier%2C+Katlyn+K%2E%22">Meier, Katlyn K.</searchLink><relatesTo>4</relatesTo><br /><searchLink fieldCode="AR" term="%22Bominaar%2C+Emile+L%2E%22">Bominaar, Emile L.</searchLink><relatesTo>4</relatesTo><i> eb7g@andrew.cmu.edu</i><br /><searchLink fieldCode="AR" term="%22Münck%2C+Eckard%22">Münck, Eckard</searchLink><relatesTo>4</relatesTo><i> emunck@cmu.edu</i><br /><searchLink fieldCode="AR" term="%22Que+Jr%2E%2C+Lawrence%22">Que Jr., Lawrence</searchLink><relatesTo>1,2</relatesTo><i> larryque@umn.edu</i>
– Name: TitleSource
  Label: Source
  Group: Src
  Data: <searchLink fieldCode="JN" term="%22Proceedings+of+the+National+Academy+of+Sciences+of+the+United+States+of+America%22">Proceedings of the National Academy of Sciences of the United States of America</searchLink>. 7/24/2012, Vol. 109 Issue 30, p11933-11938. 6p.
– Name: Subject
  Label: Subjects
  Group: Su
  Data: <searchLink fieldCode="DE" term="%22Electrons%22">Electrons</searchLink><br /><searchLink fieldCode="DE" term="%22Oxidation%22">Oxidation</searchLink><br /><searchLink fieldCode="DE" term="%22Iron+catalysts%22">Iron catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Dioxygenases%22">Dioxygenases</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+complexes%22">Metal complexes</searchLink><br /><searchLink fieldCode="DE" term="%22Bioinorganic+chemistry%22">Bioinorganic chemistry</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: Oxoiron(V) species are postulated to be involved in the mechanisms of the arene cis-dihydroxylating Rieske dioxygenases and of bioinspired nonheme iron catalysts for alkane hydroxylation, olefin cis-dihydroxylation, and water oxidation. In an effort to obtain a synthetic oxoiron(V) complex, we report herein the oneelectron oxidation of the S = 1 complex [FeIv(0)(TMC)(NCCH3)]2+ (1, where TMC is tetramethylcyclam) by treatment with tert -butyl hydroperoxide and strong base in acetonitrile to generate a metastable s = 1/2 complex 2 at -44°C, which has been characterized by UV-visible, resonance Raman, Mössbauer, and EPR methods. The defining spectroscopic characteristic of 2 is the unusual x / y anisotropy observed for the 57Fe and 170 A tensors associated with the high-valent Fe=0 unit and for the 14N A tensor of a ligand derived from acetonitrile. As shown by detailed density functional theory (DFT) calculations, the unusual x / y anisotropy observed can only arise from an iron center with substantially different spin populations in the dxz and dyz orbitals, which cannot correspond to an FeIV=0 unit but is fully consistent with an s = 1/2 Fev center, like that found for [Fev(0)(TAML)]- (where TAML is tetraamido macrocyclic ligand), the only well-characterized oxoiron(V) complex reported. Mass spectral analysis shows that the generation of 2 entails the addition of an oxygen atom to 1 and the loss of one positive charge. Taken together, the spectroscopic data and DFT calculations support the formulation of 2 as an iron(V) complex having axial oxo and acetylimido ligands, namely [Fev(0)(TMC)(NC(0)CH3)]+. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Proceedings of the National Academy of Sciences of the United States of America is the property of National Academy of Sciences and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
PLink https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=78276697
RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1073/pnas.1206457109
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 6
        StartPage: 11933
    Subjects:
      – SubjectFull: Electrons
        Type: general
      – SubjectFull: Oxidation
        Type: general
      – SubjectFull: Iron catalysts
        Type: general
      – SubjectFull: Dioxygenases
        Type: general
      – SubjectFull: Metal complexes
        Type: general
      – SubjectFull: Bioinorganic chemistry
        Type: general
    Titles:
      – TitleFull: One-electron oxidation of an oxoiron(IV) complex to form an [0=Fev=NR]+ center.
        Type: main
  BibRelationships:
    HasContributorRelationships:
      – PersonEntity:
          Name:
            NameFull: Van Heuvelen, Katherine M.
      – PersonEntity:
          Name:
            NameFull: Fiedler, Adam T.
      – PersonEntity:
          Name:
            NameFull: Shan, Xiaopeng
      – PersonEntity:
          Name:
            NameFull: De Hont, Raymond F.
      – PersonEntity:
          Name:
            NameFull: Meier, Katlyn K.
      – PersonEntity:
          Name:
            NameFull: Bominaar, Emile L.
      – PersonEntity:
          Name:
            NameFull: Münck, Eckard
      – PersonEntity:
          Name:
            NameFull: Que Jr., Lawrence
    IsPartOfRelationships:
      – BibEntity:
          Dates:
            – D: 24
              M: 07
              Text: 7/24/2012
              Type: published
              Y: 2012
          Identifiers:
            – Type: issn-print
              Value: 00278424
          Numbering:
            – Type: volume
              Value: 109
            – Type: issue
              Value: 30
          Titles:
            – TitleFull: Proceedings of the National Academy of Sciences of the United States of America
              Type: main
ResultId 1