A Reduced 2Fe2S Cluster Probe of Sulfur–Hydrogen versus Sulfur–Gold Interactions. (31st July 2015)
- Record Type:
- Journal Article
- Title:
- A Reduced 2Fe2S Cluster Probe of Sulfur–Hydrogen versus Sulfur–Gold Interactions. (31st July 2015)
- Main Title:
- A Reduced 2Fe2S Cluster Probe of Sulfur–Hydrogen versus Sulfur–Gold Interactions
- Authors:
- Crouthers, Danielle J.
Ding, Shengda
Denny, Jason A.
Bethel, Ryan D.
Hsieh, Chung‐Hung
Hall, Michael B.
Darensbourg, Marcetta Y. - Abstract:
- <abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The Ph<sub>3</sub>PAu<sup>+</sup> cation, renowned as an isolobal analogue of H<sup>+</sup>, was found to serve as a proton surrogate and form a stable Au<sub>2</sub>Fe<sub>2</sub> complex, [(μ‐SAuPPh<sub>3</sub>)<sub>2</sub>{Fe(CO)<sub>3</sub>}<sub>2</sub>], analogous to the highly reactive dihydrosulfide [(μ‐SH)<sub>2</sub>{Fe(CO)<sub>3</sub>}<sub>2</sub>]. Solid‐state X‐ray diffraction analysis found the two SAuPPh<sub>3</sub> and SH bridges in <italic>anti</italic> configurations. VT NMR studies, supported by DFT computations, confirmed substantial barriers of approximately 25 kcal mol<sup>−1</sup> to intramolecular interconversion between the three stereoisomers of [(μ‐SH)<sub>2</sub>{Fe(CO)<sub>3</sub>}<sub>2</sub>]. In contrast, the largely dative SAu bond in μ‐SAuPPh<sub>3</sub> facilitates inversion at S and accounts for the facile equilibration of the SAuPPh<sub>3</sub> units, with an energy barrier half that of the SH analogue. The reactivity of the gold‐protected sulfur atoms of [(μ‐SAuPPh<sub>3</sub>)<sub>2</sub>{Fe(CO)<sub>3</sub>}<sub>2</sub>] was accessed by release of the gold ligand with a strong acid to generate the [(μ‐SH)<sub>2</sub>{Fe(CO)<sub>3</sub>}<sub>2</sub>] precursor of the [FeFe]H<sub>2</sub>ase‐active‐site biomimetic [(μ<sub>2</sub>‐SCH<sub>2</sub>(NR)CH<sub>2</sub>S){Fe(CO)<sub>3</sub>}<sub>2</sub>].</p> </abstract>
- Is Part Of:
- Angewandte Chemie. Volume 127:Number 38(2015)
- Journal:
- Angewandte Chemie
- Issue:
- Volume 127:Number 38(2015)
- Issue Display:
- Volume 127, Issue 38 (2015)
- Year:
- 2015
- Volume:
- 127
- Issue:
- 38
- Issue Sort Value:
- 2015-0127-0038-0000
- Page Start:
- 11254
- Page End:
- 11258
- Publication Date:
- 2015-07-31
- Subjects:
- Chemistry -- Periodicals
540 - Journal URLs:
- http://onlinelibrary.wiley.com/ ↗
- DOI:
- 10.1002/ange.201504574 ↗
- Languages:
- English
- ISSNs:
- 0044-8249
- Deposit Type:
- Legaldeposit
- View Content:
- Available online (eLD content is only available in our Reading Rooms) ↗
- Physical Locations:
- British Library DSC - 0902.000000
British Library DSC - BLDSS-3PM
British Library HMNTS - ELD Digital store - Ingest File:
- 3413.xml