文摘
We have recently reported a deprotonation-induced valence inversion within a phenoxido-bridged mixed-valent diiron(II,III) complex. The initial aniline coordinated to the FeII site reacts with triethylamine, and the resulting complex contains an anilide ligand coordinated to the FeIII ion. The behavior of these complexes in acetonitrile is indeed more intricate. Owing to the very distinctive spectroscopic signatures of the complexes, the conjunction of NMR, M枚ssbauer, and UV鈥搗isible absorption spectroscopies allows one to evidence two isomerization reactions, one involving the aniline linked to FeII and the other the anilide on FeIII. Theoretical calculations sustain this conclusion. Aniline in the cis position versus the bridging phenoxide is shown to be the most stable isomer while the anilide trans to the phenoxido bridge is favored. The trans isomer of the aniline complex is more acidic than the cis one by 1 pKa unit. Isomerization of the anilide complex is 10 times faster than the analogous isomerization of the aniline complex. Both reactions are proposed to proceed through a unique mechanism. This is the first time that such isomerization reactions are evidenced in dinuclear complexes.
