Deprotonation in Mixed-Valent Diiron(II,III) Complexes with Aniline or Benzimidazole Ligands.

We have previously investigated cis/trans isomerization processes in phenoxido-bridged mixed-valent Fe(II)Fe(III) complexes that contain either one aniline or one anilide ligand. In this work, we compare the properties of similar complexes bearing one terminal protic ligand, either aniline or 1H-benzimidazole. Whatever the ligand, (1)H NMR spectroscopy clearly evidences that the complexes are present in CH3CN as a mixture of cis- and trans-isomers in a close to 1:1 ratio. We show here that addition of NEt3 indeed allows the deprotonation of these ligands, the resulting complexes bearing either anilide or benzimidazolide that are coordinated to the ferric site. The latter are singular examples of a high-spin ferric ion coordinated to a benzimidazolide ligand. Whereas the trans-isomer of the anilide complex is the overwhelming species, benzimidazolide species are mixtures of cis- and trans-isomers in equal proportions. Moreover, cyclic voltammametry studies show that Fe(III)Fe(III) complexes with 1H-benzimidazole are more stable than their aniline counterparts, whereas the reverse is observed for the deprotonated species.

Phosphoester hydrolysis: the incoming substrate turns the bridging hydroxido nucleophile into a terminal one.

Identifying the active nucleophile in hydrolysis reactions catalyzed by binuclear hydrolases is a recurrent problem and a matter of intense debate. We report on the phosphate ester hydrolysis by a Fe(III)Fe(II) complex of a binucleating ligand. This complex presents activities in the range of those observed for similar biomimetic compounds in the literature. The specific electronic properties of the Fe(III)Fe(II) complex allowed us to use (1)H NMR and Mössbauer spectroscopies to investigate the nature of the various species present in the solution in the pH range of 5-10. Both techniques showed that the hydrolysis activity is associated to a µ-hydroxido Fe(III)Fe(II) species. Further (1)H NMR experiments show that binding of anions or the substrate changes this bonding mode suggesting that a terminal hydroxide is the likely nucleophile in these hydrolysis reactions. This view is further supported by the structure determination of the hydrolysis product.