Modeling the Geometric, Electronic, and Redox Properties of Iron(III)-Containing Amphiphiles with Asymmetric [NN′O] Headgroups

Publication type:
Journal article
Metadata:
Autoren
  • Rajendra Shakya
  • Marco M Allard
  • Mara Johann
  • Mary Jane Heeg
  • Eva Rentschler
  • Jason M Shearer
  • Bruce McGarvey
  • Claudio N Verani
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000294242700058&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1021/ic2009368
eISSN
1520-510X
Externe Identifier
  • Clarivate Analytics Document Solution ID: 811UX
  • PubMed Identifier: 21805957
ISSN
0020-1669
Ausgabe der Veröffentlichung
17
Zeitschrift
INORGANIC CHEMISTRY
Paginierung
8356 - 8366
Datum der Veröffentlichung
2011
Status
Published
Titel
Modeling the Geometric, Electronic, and Redox Properties of Iron(III)-Containing Amphiphiles with Asymmetric [NN′O] Headgroups
Sub types
  • Article
Ausgabe der Zeitschrift
50

Data source: Web of Science (Lite)

Other metadata sources:
Autoren
  • Rajendra Shakya
  • Marco M Allard
  • Mara Johann
  • Mary Jane Heeg
  • Eva Rentschler
  • Jason M Shearer
  • Bruce McGarvey
  • Cláudio N Verani
DOI
10.1021/ic2009368
eISSN
1520-510X
ISSN
0020-1669
Ausgabe der Veröffentlichung
17
Zeitschrift
Inorganic Chemistry
Sprache
en
Online publication date
2011
Paginierung
8356 - 8366
Datum der Veröffentlichung
2011
Status
Published
Herausgeber
American Chemical Society (ACS)
Herausgeber URL
http://dx.doi.org/10.1021/ic2009368
Datum der Datenerfassung
2023
Titel
Modeling the Geometric, Electronic, and Redox Properties of Iron(III)-Containing Amphiphiles with Asymmetric [NN′O] Headgroups
Ausgabe der Zeitschrift
50

Data source: Crossref

Abstract
Two iron(III)-containing amphiphiles 1 and 2 have been synthesized with the [NN'O] ligands HL(tBu-ODA) (2-((octadecyl(pyridin-2-ylmethyl)amino)methyl)-4,6-di-tert-butylphenol) and HL(I-ODA) (2-((octadecyl(pyridin-2-ylmethyl)amino)methyl)-4,6-diiodophenol), respectively. Compound 1 is monometallic, whereas EXAFS data suggest that 2 is a mixture of mono- and bimetallic species. The archetypical [Fe(III)(L(NN'O))(2)](+) complexes 3-9 have been isolated and characterized in order to understand the geometric, electronic, and redox properties of the amphiphiles. Preference for a monometallic or bimetallic nuclearity is dependent on (i) the nature of the solvent used for synthesis and (ii) the type of the substituent in the phenol moiety. In methanol, the tert-butyl-, methoxy-, and chloro-substituted 3, 4, and 5 are monometallic species, whereas the bromo- and iodo-substituted 6 and 7 form bimetallic complexes taking advantage of stabilizing methoxo bridges generated by solvent deprotonation. In dichloromethane, the bromo- and iodo-substituted 8 and 9 are monometallic species; however, these species favor meridional coordination in opposition to the facial coordination observed for the tert-butyl- and methoxy-substituted compounds. Molecular structures for species 5, 7, 8, and 9 have been solved by X-ray diffraction. Furthermore, the electronic spectrum of the amphiphile 1 was expected to be similar to those of facial/cis archetypes with similar substituents, but close resemblance was observed with the profile for those meridional/cis species, suggesting a similar coordination mode. This trend is discussed based on DFT calculations, where preference for the meridional/cis coordination mode appears related to the presence of tertiary amine nitrogen on the ligand, as when a long alkyl chain is attached to the [NN'O] headgroup.
Addresses
  • Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, Michigan 48202, USA.
Autoren
  • Rajendra Shakya
  • Marco M Allard
  • Mara Johann
  • Mary Jane Heeg
  • Eva Rentschler
  • Jason M Shearer
  • Bruce McGarvey
  • Cláudio N Verani
DOI
10.1021/ic2009368
eISSN
1520-510X
Externe Identifier
  • PubMed Identifier: 21805957
Open access
false
ISSN
0020-1669
Ausgabe der Veröffentlichung
17
Zeitschrift
Inorganic chemistry
Sprache
eng
Medium
Print-Electronic
Online publication date
2011
Paginierung
8356 - 8366
Datum der Veröffentlichung
2011
Status
Published
Datum der Datenerfassung
2011
Titel
Modeling the geometric, electronic, and redox properties of iron(III)-containing amphiphiles with asymmetric [NN'O] headgroups.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
50

Data source: Europe PubMed Central

Abstract
Two iron(III)-containing amphiphiles 1 and 2 have been synthesized with the [NN'O] ligands HL(tBu-ODA) (2-((octadecyl(pyridin-2-ylmethyl)amino)methyl)-4,6-di-tert-butylphenol) and HL(I-ODA) (2-((octadecyl(pyridin-2-ylmethyl)amino)methyl)-4,6-diiodophenol), respectively. Compound 1 is monometallic, whereas EXAFS data suggest that 2 is a mixture of mono- and bimetallic species. The archetypical [Fe(III)(L(NN'O))(2)](+) complexes 3-9 have been isolated and characterized in order to understand the geometric, electronic, and redox properties of the amphiphiles. Preference for a monometallic or bimetallic nuclearity is dependent on (i) the nature of the solvent used for synthesis and (ii) the type of the substituent in the phenol moiety. In methanol, the tert-butyl-, methoxy-, and chloro-substituted 3, 4, and 5 are monometallic species, whereas the bromo- and iodo-substituted 6 and 7 form bimetallic complexes taking advantage of stabilizing methoxo bridges generated by solvent deprotonation. In dichloromethane, the bromo- and iodo-substituted 8 and 9 are monometallic species; however, these species favor meridional coordination in opposition to the facial coordination observed for the tert-butyl- and methoxy-substituted compounds. Molecular structures for species 5, 7, 8, and 9 have been solved by X-ray diffraction. Furthermore, the electronic spectrum of the amphiphile 1 was expected to be similar to those of facial/cis archetypes with similar substituents, but close resemblance was observed with the profile for those meridional/cis species, suggesting a similar coordination mode. This trend is discussed based on DFT calculations, where preference for the meridional/cis coordination mode appears related to the presence of tertiary amine nitrogen on the ligand, as when a long alkyl chain is attached to the [NN'O] headgroup.
Autoren
  • Rajendra Shakya
  • Marco M Allard
  • Mara Johann
  • Mary Jane Heeg
  • Eva Rentschler
  • Jason M Shearer
  • Bruce McGarvey
  • Cláudio N Verani
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/21805957
DOI
10.1021/ic2009368
eISSN
1520-510X
Ausgabe der Veröffentlichung
17
Zeitschrift
Inorg Chem
Sprache
eng
Country
United States
Paginierung
8356 - 8366
Datum der Veröffentlichung
2011
Status
Published
Datum, an dem der Datensatz öffentlich gemacht wurde
2011
Titel
Modeling the geometric, electronic, and redox properties of iron(III)-containing amphiphiles with asymmetric [NN'O] headgroups.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
50

Data source: PubMed

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