The copper(II) ion incorporation reactions into 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (H(2)tpfpp) to form the Cu(tpfpp) complex have been kinetically investigated with bis(beta-diketonato)copper(II) complexes (CuL2) such as bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)copper(II) (Cu(hfac)(2)), bis(1,1,1-trifluoropentane2,4-dionato)copper(II) (Cu(tfac)(2)), bis(2,2,6,6-tetramethylheptane-3,5-dionato)copper(II) (Cu(hmac)(2)), and bis(pentane-2,4-dionato)copper(H) (Cu(acac)(2)) in supercritical carbon dioxide (scCO(2)) using a previously developed stopped-flow instrument and spectrophotometric cell. Saturation dependence was observed for the conditional first-order rate constants (k(obs)) as a function of the mole fraction of excess CuL2 (x(Cu)): k(obs) = k(2)K(1)x(Cu)/(1 + K(1)x(Cu)), where K-1 is the preequilibrium constant for the fast outer sphere association between H(2)tpfpp and CuL2 and k(2) is the first-order rate constant for the rate-determining copper(II) ion incorporation into the porphyrin core. Under constant temperature (333 K) and pressure (20.0 MPa), the K-1 values are in the order of Cu(hfac)(2) < Cu(tfac)(2) < Cu(hmac)(2) < Cu(acac)(2); this trend has been interpreted by the differences in the solvation energy of the CuL2 complexes in scCO(2) and in the electrostatic repulsion between H(2)tpfpp and CuL2 anticipated in the outer sphere association complex. On the other hand, the k(2) values are in the following order: Cu(hfac)(2) > Cu(tfac)(2) > Cu(hmac)(2) > Cu(acac)(2). This order may be explained by the affinity of CuL2 for the nucleophile of the pyrrolenine nitrogen, the easiness of dissociation of the beta-diketonate ligand, and the electrostatic repulsion between H(2)tpfpp and CuL2. The thermodynamic and kinetic parameters in scCO(2) were obtained as follows: K-1 = (5.2 +/- 0.1) x 10(4) (333 K, 20.0 MPa), DeltaH(1)(o) = 76 +/- 2 kJ mol(-1) (20.0 MPa), DeltaS(1)(o) = (3.2 +/- 0.7) x 10(2) J mol(-1) K-1 (20.0 MPa), DeltaV(1)(o) = (7.9 +/- 0.6) x 10(2) cm(3) mol(-1) (333 K), k(2) = (2.7 +/-0.3) x 10(-4) s(-1) (333 K, 20.0 MPa), Delta(double dagger)H(2)(o) = -49 +/- 9 kJ mol(-1) (20.0 MPa), Delta(double dagger)S(2)(o) = (-4.6 +/- 0.3) x 10(2) J mol(-1) K-1 (20.0 MPa), and Delta(double dagger)V(2)(o) = (-4.4 +/- 0.6) x 10(2) cm(3) mol(-1) (333 K). In addition, the reaction of H(2)tpfpp with Cu(hfac)(2) has been studied in n-hexane in order to compare the results in scCO(2) with those in a conventional nonpolar solvent.