The Incorporation of Zinc Ion into a Synthetic Water-Soluble Porphyrin

T. Peter Stein, Robert A. Plane

Research output: Contribution to journalLetter

45 Citations (Scopus)

Abstract

The synthesis of a water-soluble porphyrin, C38H54N12O2. 8H2O, is described. Kinetics of the zinc incorporation of the porphyrin are reported for aqueous solutions. The rate law at fixed pH (6.23) and 30˚ is d[ZnP]/dt = (14.2 M-1 min-1)[Zn2+][H2P]. The reaction is reversible, and the first-order rate constant for zinc replacement is 1.7 × 10-4 min-1. The forward reaction is shown to be catalyzed by pyridine, 2-, 3-, and 4-methylpyridines, imidazole, and methylimidazole. Of these, imidazole shows the greatest catalysis, and it also catalyzes the reverse reaction. There is no catalysis by the sterically hindered nitrogen base collidine which serves as buffer for the rate experiments. The activation energy measured for the uncatalyzed zinc incorporation is 11.7 kcal/mole, and 12.3 kcal/mole for the pyridine-catalyzed path indicating a preequilibrium having favorable entropy. Formation and absorption spectra of metalloporphyrins of Ag(II), Sn(IV), Cu(II), In(III), and Mn(II) are also described.

Original languageEnglish (US)
Pages (from-to)607-610
Number of pages4
JournalJournal of the American Chemical Society
Volume91
Issue number3
DOIs
StatePublished - Jan 1969

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4-methylimidazole
Porphyrins
Catalysis
Zinc
Metalloporphyrins
Ions
Pyridine
Water
Entropy
Buffers
Nitrogen
Absorption spectra
Rate constants
Activation energy
Kinetics
imidazole
pyridine
Experiments
4-methylpyridine
gamma-collidine

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "The Incorporation of Zinc Ion into a Synthetic Water-Soluble Porphyrin",
abstract = "The synthesis of a water-soluble porphyrin, C38H54N12O2. 8H2O, is described. Kinetics of the zinc incorporation of the porphyrin are reported for aqueous solutions. The rate law at fixed pH (6.23) and 30˚ is d[ZnP]/dt = (14.2 M-1 min-1)[Zn2+][H2P]. The reaction is reversible, and the first-order rate constant for zinc replacement is 1.7 × 10-4 min-1. The forward reaction is shown to be catalyzed by pyridine, 2-, 3-, and 4-methylpyridines, imidazole, and methylimidazole. Of these, imidazole shows the greatest catalysis, and it also catalyzes the reverse reaction. There is no catalysis by the sterically hindered nitrogen base collidine which serves as buffer for the rate experiments. The activation energy measured for the uncatalyzed zinc incorporation is 11.7 kcal/mole, and 12.3 kcal/mole for the pyridine-catalyzed path indicating a preequilibrium having favorable entropy. Formation and absorption spectra of metalloporphyrins of Ag(II), Sn(IV), Cu(II), In(III), and Mn(II) are also described.",
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year = "1969",
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The Incorporation of Zinc Ion into a Synthetic Water-Soluble Porphyrin. / Stein, T. Peter; Plane, Robert A.

In: Journal of the American Chemical Society, Vol. 91, No. 3, 01.1969, p. 607-610.

Research output: Contribution to journalLetter

TY - JOUR

T1 - The Incorporation of Zinc Ion into a Synthetic Water-Soluble Porphyrin

AU - Stein, T. Peter

AU - Plane, Robert A.

PY - 1969/1

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N2 - The synthesis of a water-soluble porphyrin, C38H54N12O2. 8H2O, is described. Kinetics of the zinc incorporation of the porphyrin are reported for aqueous solutions. The rate law at fixed pH (6.23) and 30˚ is d[ZnP]/dt = (14.2 M-1 min-1)[Zn2+][H2P]. The reaction is reversible, and the first-order rate constant for zinc replacement is 1.7 × 10-4 min-1. The forward reaction is shown to be catalyzed by pyridine, 2-, 3-, and 4-methylpyridines, imidazole, and methylimidazole. Of these, imidazole shows the greatest catalysis, and it also catalyzes the reverse reaction. There is no catalysis by the sterically hindered nitrogen base collidine which serves as buffer for the rate experiments. The activation energy measured for the uncatalyzed zinc incorporation is 11.7 kcal/mole, and 12.3 kcal/mole for the pyridine-catalyzed path indicating a preequilibrium having favorable entropy. Formation and absorption spectra of metalloporphyrins of Ag(II), Sn(IV), Cu(II), In(III), and Mn(II) are also described.

AB - The synthesis of a water-soluble porphyrin, C38H54N12O2. 8H2O, is described. Kinetics of the zinc incorporation of the porphyrin are reported for aqueous solutions. The rate law at fixed pH (6.23) and 30˚ is d[ZnP]/dt = (14.2 M-1 min-1)[Zn2+][H2P]. The reaction is reversible, and the first-order rate constant for zinc replacement is 1.7 × 10-4 min-1. The forward reaction is shown to be catalyzed by pyridine, 2-, 3-, and 4-methylpyridines, imidazole, and methylimidazole. Of these, imidazole shows the greatest catalysis, and it also catalyzes the reverse reaction. There is no catalysis by the sterically hindered nitrogen base collidine which serves as buffer for the rate experiments. The activation energy measured for the uncatalyzed zinc incorporation is 11.7 kcal/mole, and 12.3 kcal/mole for the pyridine-catalyzed path indicating a preequilibrium having favorable entropy. Formation and absorption spectra of metalloporphyrins of Ag(II), Sn(IV), Cu(II), In(III), and Mn(II) are also described.

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