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Issue 43, 2012
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Nickel–iron dithiolates related to the deactivated [NiFe]-hydrogenases

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Described herein are preparations of synthetic models for the deactivated Ni(II)Fe(II) states of the [NiFe]-hydrogenases. Iodination of the S = ½ species [(dppe)Ni(pdt)Fe(CO)3]+ afforded the diamagnetic iodo complex [(dppe)Ni(pdt)IFe(CO)3]+. Crystallographic analysis of this species confirmed the presence of square-pyramidal Ni linked to an octahedral Fe centre. The Ni⋯Fe separation of 3.018 Å indicated the absence of metal–metal bonding. This complex could be reduced to give (dppe)Ni(pdt)Fe(CO)3 and, in the presence of iodide, decarbonylated to afford (dppe)Ni(pdt)FeI2. Derivatives of the type [(diphosphine)Ni(dithiolate)XFe(CO)2L]+ (X = Cl, Br, I) were prepared by halogenation of mixed-valence precursors [(diphosphine)Ni(dithiolate)Fe(CO)2L]+ (diphosphine = dppe, dcpe; L = tertiary phosphine or CO). The Fe(CO)2(PR3)-containing derivatives are more robust than the related tricarbonyl derivatives. Exploiting this greater stability, we characterised examples of chloride and bromide derivatives. Related fluorides could be prepared by F abstraction from BF4. Spectroscopic evidence is presented for the hydroperoxide [(dppe)Ni(pdt)(OOH)Fe(CO)2L]+, which represents a model for the Ni-SU state.

Graphical abstract: Nickel–iron dithiolates related to the deactivated [NiFe]-hydrogenases

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The article was received on 17 Aug 2012, accepted on 29 Aug 2012 and first published on 20 Sep 2012

Article type: Paper
DOI: 10.1039/C2DT31895D
Citation: Dalton Trans., 2012,41, 13324-13329
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    Nickel–iron dithiolates related to the deactivated [NiFe]-hydrogenases

    D. Schilter and T. B. Rauchfuss, Dalton Trans., 2012, 41, 13324
    DOI: 10.1039/C2DT31895D

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