Functionalized nickel(II)-iron(II) dithiolates as biomimetic models of [NiFe]-H₂ases

To develop the structural and functional modeling chemistry of [NiFe]-H₂ases, a series of new biomimetics for the active site of [NiFe]-H₂ases have been prepared by various synthetic methods. Treatment of the mononuclear Ni complex (pnp)NiCl₂ (pnp = (Ph₂PCH₂)₂NPh) with (dppv)Fe(CO)₂(pdt) (dppv = 1,2-(Ph₂P)₂C₂H₂, pdt = 1,3-propanedithiolate) and KPF₆ gave the dicarbonyl complex [(pnp)Ni(pdt)Fe(CO)₂(dppv)](PF₆)₂ ([1](PF₆)₂). Further treatment of [1](PF₆)₂ and [(dppe)Ni(pdt)Fe(CO)₂(dppv)](BF₄)₂ (dppe = 1,2-(Ph₂P)₂C₂H₄) with the decarbonylation agent Me₃NO and pyridine afforded the novel sp³ C-Fe bond-containing complexes [(pnp)Ni(SCH₂CH₂CHS)Fe(CO)(dppv)]PF₆ ([2]PF₆) and [(dppe)Ni(SCH₂CH₂CHS)Fe(CO)(dppv)]BF₄ ([3]BF₄). More interestingly, the first t-carboxylato complexes [(pnp)Ni(pdt)Fe(CO)(t-O₂CR)(dppv)]PF₆ ([4]PF₆, R = H; [5]PF₆, R = Me; [6]PF₆, R = Ph) could be prepared by reactions of [1]PF₆ with the corresponding carboxylic acids RCO₂H in the presence of Me₃NO, whereas further reactions of [4]PF₆-[6]PF₆ with aqueous HPF₆ and 1.5 MPa H₂ gave rise to the μ-hydride complex [(pnp)Ni(pdt)Fe(CO)(μ-H)(dppv)]PF₆ ([7]PF₆). Except for H₂ activation by t-carboxylato complexes [4]PF₆-[6]PF₆ to give a μ-hydride complex ([7]PF₆), the sp³ C-Fe bond-containing complex [2]PF₆ was found to be a catalyst for proton reduction to H₂ under CV conditions. Furthermore, the chemical reactivity of the μ-hydride complex [7]PF₆ displayed in the e^- transfer reaction with FcPF₆ in the presence of CO, the H₂ evolution reaction with the protonic acid HCl, and the H^- transfer reaction with N-methylacridinium hexafluorophosphate ([NMA]PF₆) was systematically studied. As a result, a series of the expected products such as H₂, ferrocene, the dicarbonyl complex [1](PF₆)₂, the μ-chloro complex [(pnp)Ni(pdt)Fe(CO)(μ-Cl)(dppv)]PF₆ ([8]PF₆), the t-MeCN-coordinated complex [(pnp)Ni(pdt)Fe(CO)(t-MeCN)(dppv)](PF₆)₂ ([9](PF₆)₂) and the H^- transfer product AcrH₂ were produced. While all the newly prepared model complexes were structurally characterized by spectroscopic methods, the molecular structures of some of their representatives were confirmed by X-ray crystallography.