Formation and Deprotonation Kinetics of the Sitting-Atop Complex of Copper(II) Ion with 5,10,15,20-Tetraphenylporphyrin Relevant to the Porphyrin Metalation Mechanism. Structure of Copper(II)-Pyridine Complexes in Acetonitrile As Determined by EXAFS Spectroscopy

Article abstract of DOI:10.1021/ic980420d

The formation of a sitting-atop (SAT) complex of Cu(II) ion with 5,10,15,20-tetraphenylporphyrin (H₂tpp) in acetonitrile has been observed, and the kinetic parameters for the formation were determined as follows; k_so = (3.6 ±0.1) × 10⁵ mol^-1dm³ at 25.0 °C, ΔH^so? = 56 ±5 kJ mol^-1, and ΔS_SO? = 46 ±19 J mol^-1 K^-1. The ¹H NMR spectrum of the SAT complex (Cu(H₂tpp)²⁺) indicated that two pyrrolenine nitrogens coordinate to the Cu(II) ion and that two protons bound to the pyrrole nitrogens remain. The protons were abstracted by the addition of pyridine (py) as the Br?nsted base to give the Cu(tpp) metalloporphyrin. In the presence of py, the product for the reaction of the Cu(II) ion with H₂tpp was Cu(tpp) instead of the SAT complex. The observed conditional rates for the formation of Cu(H₂tpp)²⁺ and Cu(tpp) were interpreted by the contribution of Cu²⁺, Cu(py)²⁺, and Cu(py)₂²⁺ species, and the second-order rate constants of the SAT complex formation were k_S1 = (3.5 ± 0.3) × 10⁴ mo^-1 dm³ s^-1 for Cu(py)²⁺ and k_S2 = 90 ± 2 mol^-1 dm³ s^-1 for Cu(py)₂²⁺. Deprotonation rates were measured by following the reaction between the SAT complex and py as a function of the py concentration, and the second-order rate constant was determined to be (2.3 ± 0.1) × 10² mol^-1 dm³ s^-1. The present kinetic results have indicated that the SAT complex exists during the course of the metalation process and that the SAT complex formation is a rate-determining step.