uu.seUppsala University Publications
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Coordination and conformational isomers in mononuclear iron complexes with pertinence to the [FeFe] hydrogenase active site
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
Show others and affiliations
2014 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 43, no 11, 4537-4549 p.Article in journal (Refereed) Published
Abstract [en]

A series of six mononuclear iron complexes of the type [Fe(X-bdt)((P2N2Ph)-N-R)(CO)] ((P2N2Ph)-N-R = 1,5-diaza-3,7-diphosphaoctane, bdt = benzenedithiolate with X = H, Cl-2 or Me and R = Ph, Bn, Cyc or tert-Bu) was prepared. This new class of penta-coordinate iron complexes contains a free coordination site and a pendant base as essential structural features of the [FeFe]-hydrogenase active site. The bidentate nature of the (P2N2Ph)-N-R ligands was found to be crucial for the preferential formation of coordinatively unsaturated penta-coordinate complexes, which is supported by first principle calculations. IR-spectroscopic data suggest the presence of coordination isomers around the metal center, as well as multiple possible conformers of the (P2N2Ph)-N-R ligand. This finding is further corroborated by X-ray crystallographic and computational studies. P-31{H-1}-NMR- and IR-spectroscopic as well as electrochemical measurements show that the electronic properties of the complexes are strongly, and independently, influenced by the P-substituents at the (P2N2Ph)-N-R ligand as well as by modifications of the bdt bridge. These results illustrate the advantages of this modular platform, which allows independent and selective tuning through site specific modifications. Potential catalytic intermediates, namely singly reduced and protonated complexes, have been further investigated by spectroscopic methods and exhibit remarkable stability. Finally, their general capacity for electro-catalytic reduction of protons to molecular hydrogen was verified.

Place, publisher, year, edition, pages
2014. Vol. 43, no 11, 4537-4549 p.
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:uu:diva-221722DOI: 10.1039/c3dt53268bISI: 000332389700041OAI: oai:DiVA.org:uu-221722DiVA: diva2:710191
Available from: 2014-04-04 Created: 2014-04-03 Last updated: 2017-12-05Bibliographically approved

Open Access in DiVA

fulltext(1854 kB)406 downloads
File information
File name FULLTEXT01.pdfFile size 1854 kBChecksum SHA-512
f7dbe1b05f0775a0174d226a56d9e4a88dbe1988a32e903e1a206a841f9db74f396cdd8436f243d5ad90e52e58bd161d81cc6539e5e4f1ad13e2f6bfd4419b19
Type fulltextMimetype application/pdf

Other links

Publisher's full text

Authority records BETA

Orthaber, AndreasStreich, DanielOtt, Sascha

Search in DiVA

By author/editor
Orthaber, AndreasStreich, DanielOtt, Sascha
By organisation
Molecular BiomimeticsPhysical Chemistry
In the same journal
Dalton Transactions
Natural Sciences

Search outside of DiVA

GoogleGoogle Scholar
Total: 406 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 875 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf