1284 E. 33. FLEISCHER, E.I. CHOI,P. HAMBRIGHT, AND A. STONE
Inorganic Chemistry
CONTRIBUTIOS FROM THE
GEORGE HERBERT
JONES LABORATORY,
UXIVERSITY OF CHICAGO, CHICAGO 37, ILLINOIS
Porphyrin Studies : Kinetics of Metalloporphyrin Formation1 BY EVERLY B. FLEISCHER, E. I. CHOI, PETER HAMBRIGHT,
AND
ALLEN STOSE
Receined January 15, 1964 A mechanism for the formation of metalloporphyrins in aqueous solutions is formulated for tetrapyridylporphinc. The order of reactivity of metals toward metalloporphyrin formation is Cu(I1) > Zn(I1) > Mn(I1) > Co(I1) > Fe(I1) > Si(I1) > Cd(I1). T h e equilibrium constant for the equilibrium between tetrapyridylporphine, metal ion, and the porphyrin sitting-atop complex is measured for various ions.
Previous studies have dealt with the kinetic and equilibrium properties of the porphyrin molecule. 2-g The reaction of metal ions with the porphyrin nucleus to form metalloporphyrin complexes was investigated with the purpose of determining the mechanism of the reaction and the order of reactivity of various metal ions. The over-all reaction is given in eq. 1.lo TPyPHz
+ M(Hz0)6’+
4
M-TPyP(H20)z f 2H+
+ 4Ha0
(1)
Results The rates of formation of metalloporphyrins were studied in the pH range 1.5-2.4. In this pH range tetrapyridylporphine exists predominantly in the free base form.12 The sitting-atop complex of tetrapyridylporphine is formed in the range of metal concentrations used in this study.4,11 The spectra that clearly demonstrate the existence of a porphyrin species that is not either the free base or diacid porphyrin are shown in Fig. 1. Curve 1 is the spectrum of tetrapyridylporphine free base a t a pH of 2.2. Curve 2 is the spectrum of the tetrapyridylporphine diacid in 1.0 M HN03. Curve 3 is the spectrum of tetrapyridylporphine with sodium ions a t a pH of 2.2 and 4.0 M sodium nitrate. The spectra of other sitting-atop complexes of tetrapyridylporphine in aqueous solution are similar to the sodium spectrum. The spectra of a series of solutions of constant porphyrin and varying sodium ion show isosbestic points a t 418, 498, and 536 mp. The Soret region, from 380 to 480 mp, of such a series of varying sodium ion concentrations from 0 to 4.0 M with con(1) This work mas supported by a Public Health Service Grant and by t h e Louis Block Fund. ( 2 ) E. B. Fleischer, I n o r g . Chem., 1, 493 (1962). (3) E. I. Choi and E. B. Fleischer, ibid., 2, 94 (1963). (4) E. B, Fleischer and I.. E. Webb, J . Phys. Chein., 67, 1131 (1963). ( 5 ) M , B. Lowe and 5. S.Phillips, S a l u i e , 190, 262 (1960). (6) W. S. Caughey and A. H. Corwin, J . A m . Chem. Soc., 77, 1509 (19.55). (7) A. H. Corwin and P. U’ei, J . Oip. Chem., 27, 4286 (1962). ( 8 ) A. H. Corwin and R. Singh, i b i d . , 28, 2476 (1963). (9) J. X , Phillips, Rea. Piwe A p p l . Chem., 10, 35 (1960). (10) T h e following conventions are used in this paper. TPyPHz stands for a,P,y,6-tetra(4-pyridyl)porphineand will be called tetrapyi-idylporphine. T P y P H i * * stands for t h e tetrapyridylporphine diacid. M - T P y P stands for the tetrapyridylporphine metal complex. M-SAT-TPyPH22- stands for the tetrapyridylporphine sitting-atop complex.” T h e charges refer only t o the porphyrin nucleus and not t o the molecule as a whole. T h e tetrapyridylporphine in acid aqueous solution always has four charges due t o t h e protons t h a t are on t h e pyridyl groups. (11) E. B. Fleischer and J. H . \
