MPI für bioanorganische Chemie / MPI für bioanorganische Chemie |
|Light-Atom Influences on the Electronic Structures of Iron Sulfur Clusters|
|Authors:||Pollock, Christopher J.; Tan, Lay Ling; Zhang, Wei; Lancaster, Kyle M.; Lee, Sonny C.; DeBeer, Serena|
|Date of Publication (YYYY-MM-DD):||2014|
|Title of Journal:||Inorganic Chemistry|
|Issue / Number:||5|
|Review Status:||Internal review|
|Abstract / Description:||Ligand K-edge X-ray absorption spectroscopy was used to study dimeric and tetrameric Cl-terminated Fe-S clusters with variable numbers of S2- substituted by (NBu2-)-Bu-t ((NBu2-)-Bu-t = tertbutylimido) ligands to gain insights into the functional role of the interstitial light atom in the iron-molybdenum cofactor (FeMoco) of nitrogenase. These studies are complemented by time-dependent density functional theory analysis to quantify the relative effects on Fe-S and Fe-Cl bonding. The results show that (NBu2-)-Bu-t substitution dramatically affects the electronic structure of dimeric clusters, while the impact on tetrameric clusters is small. Strong agreement between experiment and theory merited extension of this analysis to hypothetical clusters with S2- substituted by N and C-atom donor ligands as well as FeMoco itself. These results show that very strong electron donors are required to appreciably modulate the electronic structure of tetrameric (or larger) iron sulfur clusters, pointing to a possible role of the central C4- in FeMoco.|
|External Publication Status:||published|
|Communicated by:||N. N.|
|Affiliations:||MPI für bioanorganische Chemie|
|External Affiliations:||[Tan,L.L.;Zhang,W.;Lee,S.C.;] Univ Waterloo, Dept.Chem., Waterloo, ON N2L 3G1, Canada.
[Lancaster,K.M.; ] Cornell Univ., Dept.Chem.& Biol.Chem., Ithaca, NY 14853 USA.
|Identifiers:||ISI:000332348200033 [ID No:1] |
ISSN:0020-1669 [ID No:2]
DOI:10.1021/ic402944r [ID No:3]
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