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

Chemical Science
Allen M LunsfordM Y Darensbourg

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 ...Continue Reading

References

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Citations

Jun 22, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Pokhraj GhoshMarcetta Y Darensbourg
Oct 28, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Takehiko ShimamuraTsutomu Mizuta
Aug 17, 2020·Proceedings of the National Academy of Sciences of the United States of America·Oliver LampretThomas Happe
Nov 15, 2017·Journal of the American Chemical Society·Hao Tang, Michael B Hall
Jul 14, 2018·Journal of the American Chemical Society·Debangsu SilMarcetta Y Darensbourg

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Methods Mentioned

BETA
X-ray
column chromatography
bio-hybrid

Software Mentioned

HYSCORE
SAINT
ORCA
SHELXTL
Easyspin
Seed
Gaussian

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