Heterodinuclear nickel(ii)–iron(ii) azadithiolates as structural and functional models for the active site of [NiFe]-hydrogenases

Abstract

To develop the biomimetic chemistry of [NiFe]-H₂ases, the first azadithiolato-bridged NiFe model complexes [CpNi{(μ-SCH₂)₂NR}Fe(CO)(diphos)]BF₄ (5, R = Ph, diphos = dppv; 6, 4-ClC₆H₄, dppv; 7, 4-MeC₆H₄, dppv; 8, CO₂CH₂Ph, dppe; 9, H, dppe) have been synthesized via well-designed synthetic routes. Thus, treatment of RN[CH₂S(O)CMe]₂ with t-BuONa followed by reaction of the resulting intermediates RN(CH₂SNa)₂ with (dppv)Fe(CO)₂Cl₂ or (dppe)Fe(CO)₂Cl₂ gave the N-substituted azadithiolato-chelated Fe complexes [RN(CH₂S)₂]Fe(CO)₂(diphos) (1, R = Ph, diphos = dppv; 2, 4-ClC₆H₄, dppv; 3, 4-MeC₆H₄, dppv; 4, CO₂CH₂Ph, dppe). Further treatment of 1–4 with nickelocene in the presence of HBF₄·Et₂O afforded the corresponding N-substituted azadithiolato-bridged NiFe model complexes 5–8, while treatment of 8 with HBF₄·Et₂O resulted in formation of the parent azadithiolato-bridged model complex 9. While all the new complexes 1–9 were characterized by elemental analysis and spectroscopy, the molecular structures of model complexes 6–8 were confirmed by X-ray crystallographic study. In addition, model complexes 7 and 9 were found to be catalysts for H₂ production with moderate i_cat/i_p and overpotential values from TFA under CV conditions.