Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics of the Formation of Metalloporphyrins and the Catalytic Effect of Lead Ions and Hydrogen Ions

  • Qi, Yong (College of Chemistry And Chemical Engineering, Shan Xi University) ;
  • Pan, Ji Gang (College of Chemistry And Chemical Engineering, Shan Xi University)
  • Received : 2014.03.17
  • Accepted : 2014.07.31
  • Published : 2014.11.20
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Abstract

The reaction mechanism of Lead ions catalyzing complexation reactions between TIPP and metal ions was investigated by researching the kinetics of the formation of metalloporphyrins by UV/Vis-spectra, and verified by exploring the formation of metalloporphyrins catalyzed by acetic acid. Kinetics studies suggested that the fluctuations of reaction rate indicated the formation of metalloporphyrin was step-wise, including the pre-equilibrium step (the coordination of the pyrrolenine nitrogens to $Mn^+$) and the rate-controlling step (the deprotonation of the pyrrole proton). In the pre-equalization step, a sitting-atop (SAT) structure formed first with the complexation between larger radius of $Pb^{2+}$ and TIPP, changed the activation, then $Pb^{2+}$ left with the smaller radius of metal ions attacking from the back of the porphyrin ring center. In the rate-controlling step, two pyrrole protons dissociated to restore a stable structure. This was verified by adding acetic acid at different reaction times.

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