Dynamic study of metal-ion incorporation into porphyrins based on the dynamic characterization of metal ions and on sitting-atop complex formation.
We succeeded in the detection of the sitting-atop (SAT) copper(II) complex of TPP (5,10,15,20-tetraphenylporphyrin) in acetonitrile (AN) as a solvent with a very low Brønsted basicity, where two pyrrolenine nitrogens in the Cu(II)-SAT complex coordinate to the metal ion and two protons still remain on the pyrrole nitrogens. The structure parameters around the copper(II) ion in the Cu(II)-SAT complex, as determined by a fluorescent EXAFS method, suggest an axially elongated and equatorially distorted six-coordinate geometry. We measured the rates of the formation reaction of the SAT complexes for a series of transition metal(II) ions in AN using the stopped-flow technique. We propose the mechanism where there is a rapid deformation equilibrium of the porphyrin ring prior to the rate-determining step of the bond rupture of a coordinated solvent molecule on the metal(II) ion. Furthermore, we measured the rates of the deprotonation reaction of the Cu(II)-SAT complex by some Brønsted bases and indicated that the rate-determining step is the attack of the base on the proton of the pyrrole nitrogen in the SAT complex. Finally, a unified mechanism relevant to the porphyrin metalation mechanism has been proposed.
Funahashi
S
S
Laboratory of Analytical Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan. sfuna@chem4.chem.nagoya-u.ac.jp
Inada
Y
Y
Inamo
M
M
D007700:Kinetics; D008670:Metals / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*
D008670:Metals; D011166:Porphyrins