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  Spectroscopic and Quantum Chemical Investigation of Benzene-1,2-dithiolate-Coordinated Diiron Complexes with Relevance to Dinitrogen Activation

Kalläne, S. I., Hahn, A. W., Weyhermüller, T., Bill, E., Neese, F., DeBeer, S., et al. (2019). Spectroscopic and Quantum Chemical Investigation of Benzene-1,2-dithiolate-Coordinated Diiron Complexes with Relevance to Dinitrogen Activation. Inorganic Chemistry, 58(8), 5111-5125. doi:10.1021/acs.inorgchem.9b00177.

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Kalläne, Sabrina I.1, Author           
Hahn, Anselm W.2, Author           
Weyhermüller, Thomas1, Author           
Bill, Eckhard2, Author           
Neese, Frank1, 3, Author           
DeBeer, Serena2, Author           
van Gastel, Maurice1, 4, Author           
Affiliations:
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
2Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023871              
3Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              
4Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541713              

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 Abstract: In this work, a benzene-1,2-dithiolate (bdt) pentamethylcyclopentadienyl di-iron complex [Cp*Fe(μ–η24-bdt)FeCp*] and its [Cp*Fe(bdt)(X)FeCp*] analogues (where X = N2H2, N2H3, H, NH2, NHCH3, or NO+) were investigated through spectroscopic and computational studies. These complexes are of relevance as model systems for dinitrogen activation in nitrogenase and share with its active site the presence of iron, sulfur ligands, and a very flexible electronic structure. On the basis of a combination of X-ray emission spectroscopy (XES), X-ray crystallography, Mössbauer, NMR, and EPR spectroscopy, the geometric and electronic structure of the series has been experimentally elucidated. All iron atoms were found to be in a local low-spin configuration. When no additional X ligand is bound, the bdt ligand is tilted and features a stabilizing π-interaction with one of the iron atoms. The number of lone-pair orbitals provided by the nitrogen-containing species is crucial to the overall electronic structure. When only one lone-pair is present and the iron atoms are bridged by one atom, a three-center bond occurs, and a direct Fe–Fe bond is absent. If the bridging atom provides two lone-pairs, then an Fe–Fe bond is formed. A recurring theme for all ligands is σ-donation into the unoccupied eg manifolds of both iron atoms and back-donation from the t2g manifolds into the ligand π* orbitals. The latter results in a weakening of the double bond of the bound ligand, and in the case of NO+, it results in a weakening of all bonds that comprise triple bond. The electron-rich thiolates further amplify this effect and can also serve as bases for proton binding. While the above observations have been made for the studied di-iron complexes, they may be of relevance for the active site in nitrogenase, where a similar N2 binding mode may occur allowing for the simultaneous weakening of the N2 σ bond and π bonds.

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Language(s): eng - English
 Dates: 2019-01-212019-03-252019-04-15
 Publication Status: Published in print
 Pages: 15
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.9b00177
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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 58 (8) Sequence Number: - Start / End Page: 5111 - 5125 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669