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

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Kalläne,  Sabrina I.
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Hahn,  Anselm W.
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Weyhermüller,  Thomas
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Bill,  Eckhard
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Neese,  Frank
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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DeBeer,  Serena
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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van Gastel,  Maurice
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

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.


Cite as: https://hdl.handle.net/21.11116/0000-0006-4013-C
Abstract
In this work, a benzene-1,2-dithiolate (bdt) pentamethylcyclopentadienyl di-iron complex [Cp*Fe(mu-eta(2):eta(4)-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, Mossbauer, 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 pi-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 sigma-donation into the unoccupied e(g) manifolds of both iron atoms and back-donation from the t(2g) manifolds into the ligand pi* 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 N-2 binding mode may occur allowing for the simultaneous weakening of the N-2 sigma bond and pi bonds.