Nickel-iron dithiolates related to the deactivated [NiFe]-hydrogenases

David Schilter, Thomas B. Rauchfuss

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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 = 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. This journal is

Original languageEnglish (US)
Pages (from-to)13324-13329
Number of pages6
JournalDalton Transactions
Issue number43
StatePublished - Nov 21 2012

ASJC Scopus subject areas

  • Inorganic Chemistry


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