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Published on: March 19, 2020
Characterization of Complex-B ([Fe(κ3-cys)(CN)(CO)2]-), Biosynthetic Precursor to the [FeFe]-Hydrogenase Active Site,
Xin Yu1, Toby J Woods1, Thomas B Rauchfuss1
1School of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, United States.
Abstract:
The preparation, spectroscopy, and structure are described for [Fe(κ3-cys)(CN)(CO)2]- ([2]-). Otherwise known as complex-B, this coordination complex is an early intermediate in the biosynthesis of the active site of the [FeFe]-hydrogenases. As confirmed by X-ray crystallography, the complex is octahedral with a tridentate cysteinate ligand. The octahedron is completed with two CO ligands and CN-, which is trans to thiolate. A second isomer is observed in solution. Complex [2]- was prepared by treating [Fe(succinimido)(Br)(CN)(CO)3]- ([1]-) with cysteinate. From [1]- the related penicillamine and homocysteine complexes were also prepared. A practical reagent for probing the biosynthetic role of complex-B, called Syn-B-Br, can be produced in good yield from [1]-. Complex [1]- is prepared by oxidative addition of N-bromosuccinimide to [Fe(CN)(CO)4]-. The work is complemented by 13CO exchange experiments and DFT calculations.
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