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Effect of Bridgehead Steric Bulk on the Intramolecular C-H Heterolysis of [FeFe]-Hydrogenase Active Site Models Containing a P2N2 Pendant Amine Ligand
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2016 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 55, no 2, 411-418 p.Article in journal (Refereed) PublishedText
Abstract [en]

A series of pendant amine-containing [FeFe]-hydrogenase models, [X(CH2S-μ)2{Fe(CO)3}{Fe(CO)(P2 PhN2 Bn)}] (1H, X = CH2; 2Me, C(CH3)2; 3Et, C(CH2CH3)2; and P2 PhN2 Bn = 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) with different groups at the bridgehead carbon of the S-to-S linker were synthesized. The oxidations of these complexes as well as the reverse reduction reaction were studied by cyclic voltammetry and in situ IR spectroscopy. Regardless of the bridgehead steric bulk, all three complexes demonstrate intramolecular iron-mediated C(sp3)-H bond heterolytic cleavage with the assistance of the pendant amine base within the chelating diphosphine ligand in the two-electron oxidation process. X-ray crystallographic analysis shows that the doubly oxidized products, [1′H]+, [2′Me]+, and [3′Et]+, all have a rigid FeSC three-membered ring at the open apical site of the rotated iron center. The most noticeable difference in structures of the oxidized complexes is that the single CO ligand of the rotated Fe(P2 PhN2 Bn)(CO) unit in [1′H]+ and [2′Me]+ is found below the Fe⋯Fe vector, while in [3′Et]+ an unusually rotated Fe(P2 PhN2 Bn)(CO) moiety positions one of the P donors within the bidentate ligand under the Fe⋯Fe vector. The starting FeIFeI complexes can be recovered from their corresponding doubly oxidized complexes by reduction in the presence of Brönsted acid.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2016. Vol. 55, no 2, 411-418 p.
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Chemical Sciences
URN: urn:nbn:se:kth:diva-184052DOI: 10.1021/acs.inorgchem.5b00923ISI: 000369211700006PubMedID: 26230977ScopusID: 2-s2.0-84955466080OAI: diva2:914269

QC 20160323

Available from: 2016-03-23 Created: 2016-03-22 Last updated: 2016-03-23Bibliographically approved

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Sun, Licheng
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