NDLI: Cyanide-bridged iron complexes as biomimetics of tri-iron arrangements in maturases of the H cluster of the di-iron hydrogenase

Content Provider	Royal Society of Chemistry (RSC)
Author	Ding, Shengda Erdem, Özlen F. Lunsford, Allen M. Wang, Ning Beto, Christopher C. Bhuvanesh, Nattamai Hall, Michael B. Darensbourg, Marcetta Y.
Copyright Year	2016
Abstract	Developing from certain catalytic processes required for ancient life forms, the H2 processing enzymes [NiFe]- and [FeFe]-hydrogenase (H2ase) have active sites that are organometallic in composition, possessing carbon monoxide and cyanide as ligands. Simple synthetic analogues of the 2Fe portion of the active site of [FeFe]-H2ase have been shown to dock into the empty carrier (maturation) protein, apo-Hyd-F, via the bridging ability of a terminal cyanide ligand from a low valent FeIFeI unit to the iron of a 4Fe4S cluster of Hyd-F, with spectral evidence indicating CN isomerization during the coupling process (Berggren, et al., Nature, 2013, 499, 66–70). To probe the requirements for such cyanide couplings, we have prepared and characterized four cyanide-bridged analogues of 3-Fe systems with features related to the organoiron moiety within the loaded HydF protein. As in classical organometallic chemistry, the orientation of the CN bridge in the biomimetics is determined by the precursor reagents; no cyanide flipping or linkage isomerization was observed. Density functional theory computations evaluated the energetics of cyanide isomerization in such [FeFe]–CN–Fe ⇌ [FeFe]–NC–Fe units, and found excessively high barriers account for the failure to observe the alternative isomers. These results highlight roles for cyanide as an unusual ligand in biology that may stabilize low spin iron in [FeFe]-hydrogenase, and can act as a bridge connecting multi-iron units during bioassembly of the active site.
Starting Page	3710
Ending Page	3719
Page Count	10
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	7
Issue Number	6
Journal	Chemical Science
DOI	10.1039/c6sc00213g
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Energetics Cyanide Ligand Active site Isomerization Spectral evidence Berggren Protein Hydrogenase Biomimetics NC Organometallic chemistry Classical mechanics Density functional theory Carbon monoxide Molecular biology
Content Type	Text
Resource Type	Article
Subject	Chemistry

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