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Restricted rotation of an Fe(CO)2(PL3)-subunit in [FeFe]-hydrogenase active site mimics by intramolecular ligation

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Abstract

A new series of homodinuclear iron complexes as models of the [FeFe]-hydrogenase active site was prepared and characterized. The complexes of the general formula [Fe2(mcbdt)(CO)5PPh2R] (mcbdt = benzene-1,2-dithiol-3-carboxylic acid) feature covalent tethers that link the mcbdt ligand with the phosphine ligands which are terminally coordinated to one of the Fe centres. The synthetic feasability of the concept is demonstrated with the preparation of three novel complexes. A detailed theoretical investigation showes that by introducing a rigid covalent link between the phosphine and the bridging dithiolate ligands, the rotation of the Fe(CO)2P unit is hindered and higher rotation barriers were calculated compared to non-linked reference complexes. The concept of restricting Fe(L)3 rotation is an approach to kinetically stabilize terminal hydrides which are reactive intermediates in catalytic proton reduction cycles of the enzymes.

Graphical abstract: Restricted rotation of an Fe(CO)2(PL3)-subunit in [FeFe]-hydrogenase active site mimics by intramolecular ligation

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Publication details

The article was received on 29 Dec 2018, accepted on 21 Feb 2019 and first published on 21 Feb 2019


Article type: Paper
DOI: 10.1039/C8DT05148H
Citation: Dalton Trans., 2019, Advance Article
  • Open access: Creative Commons BY-NC license
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    Restricted rotation of an Fe(CO)2(PL3)-subunit in [FeFe]-hydrogenase active site mimics by intramolecular ligation

    S. Pullen, S. Maji, M. Stein and S. Ott, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C8DT05148H

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