Kinetics and mechanisms of metalloporphyrin reactions

Lavallee, David K.

doi:10.1016/0010-8545(85)80002-3

Cited by 120 publications

(70 citation statements)

References 185 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…To explain the effect of solvent on protonation of TPPS based on the KAT solvent parameters, logK 1 , logK 2 F and r 2 are squared correlation coefficient and F-statistic values respectively. The number in bracket shows the standard deviation of each regression coefficient.…”

Section: Solvent Effectsmentioning

confidence: 99%

“…Due to little experimental data in these ranges, protonation constants were correlated only with one KAT parameter. The best fitted models were obtained as logK 2 It is interesting to verify the effect of nonspecific interactions by analyzing data with the Born's electrostatic model [29,31]. Born's model was examined by plotting protonation constant as a function of the reciprocal dielectric constant of the mixture in Figure 5.…”

Section: Solvent Effectsmentioning

confidence: 99%

“…Various biological and industrial applications of porphyrins made them interesting compounds [1][2][3]. Among porphyrin derivatives, 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin, TPPS, is well-known.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Solvent effect on protonation of tpps in water-DMF mixtures

Farajtabar¹,

Faeli²

2017

Bull. Chem. Soc. Eth.

View full text Add to dashboard Cite

ABSTRACT. The protonation of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin was investigated in aqueous solutions of N,N-dimethyformamide at 25 C and 0.1 mol.dm -3 sodium perchlorate. The solvent effect on value of protonation constant was examined by using the linear solvation energy relationship concept. The value of logK1, logK2 and logKt was correlated with the macroscopic (dielectric constant) and microscopic Kamlet-Taft parameters (,  and *) of binary mixtures. The solvent effects were analyzed in the terms of Kamlet, Abboud and Taft model (KAT). Multiple linear regression were used to find the contribution of the microscopic parameters containing  (hydrogen-bond acidity), * (dipolarity/polarizability) and  (hydrogen-bond basicity). It was found that  and  were the most predominant descriptors. Also, relationship with reciprocal of dielectric constant was obtained based on Born's model, showing the significance of specific solute-solvent interactions. Therefore the hydrogen bonding interactions between solute and solvent components are mainly responsible for the change in protonation constants of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin in water-N,N-dimethyformamid binary mixtures.

show abstract

Section: Solvent Effectsmentioning

confidence: 99%

Section: Solvent Effectsmentioning

confidence: 99%

See 1 more Smart Citation

Solvent effect on protonation of tpps in water-DMF mixtures

Farajtabar¹,

Faeli²

2017

Bull. Chem. Soc. Eth.

View full text Add to dashboard Cite

show abstract

“…The rate of metalation of N-alkylporphyrins is much faster than that of non-N-alkylporphyrins due to distortion of the porphyrin plane by the sp 3 hybridization of one of the pyrrolenic nitrogens [1][2][3][4]. Therefore, N-alkylporphyrin is an important model for ferrochelatase, which catalyses the biological insertion of Fe(II) into protoporphyrin IX by ring distortion.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, N-alkylporphyrin is an important model for ferrochelatase, which catalyses the biological insertion of Fe(II) into protoporphyrin IX by ring distortion. The mechanism of metalation of N-substituted porphyrins (M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)) has been studied both in aqueous and nonaqueous media [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanisms of the formation of a sitting-atop complex of N-alkylporphyrin with Al(III) in moist acetonitrile

Tsukahara

Onoue

Fujiwara

2001

J. Porphyrins Phthalocyanines

View full text Add to dashboard Cite

ABSTRACT:The formation of a sitting-atop complex of a N-alkylporphyrin, containing a 6-hydroxyhexyl group, with Al 3 was studied in moist acetonitrile by equilibrium and kinetic measurements. A sandwich type of metalloporphyrin, where a metal ion binds two N-alkylporphyrins, appears to be formed under the conditions that porphyrins exist in excess over a metal ion. When a large excess of metal ion was used, a 1:1 type of sitting-atop complex of Al(III) N-alkylporphyrin was produced through formation of the sandwich type of Al(III) Nalkylporphyrin.

show abstract

Kinetics and Mechanism of the Reaction of Mercury(II) with a Water-soluble Octabromoporphyrin

Nahar

Tabata

1998

J. Porphyrins Phthalocyanines

View full text Add to dashboard Cite

The reaction of mercury(II) hydroxide with 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin, [Formula: see text]( H 2P4−), to form the mercury(II) porphyrin [( TPPSBr 8) Hg ]4−( HgP 4−) was investigated in the pH range 6.2-8.5. The observed rate constant was first-order with respect to the mercury(II) concentration and decreased with increasing pH from pH 6.2 to 7.5 and then increased from pH 7.5 to 8.5. The rate expression was written as d [ HgP 4−]/dt = (kHPK−1[ H +]−1 + k H 2 P + k H 3P K 1[ H +])(1 + K1[ H +] + K−1[ H +]−1)−1[ Hg ( OH )2][ H 2 P 4−]. The kHP, kH2P and kH3P values were found to be (1.33 ± 0.02) × 108, (5.50 ± 0.08) × 106 and (1.40 ± 0.08) × 108 M −1 s−1 respectively, with K1 = [ H 3 P 3−][ H 2 P 4−]−1[ H +]−1 = 104.83 ± 0.04 and K−1 = [ HP 5−][ H +][ H 2 P 4−]−1 = 1010.02 ± 0.02. The activation parameters were [Formula: see text] and ΔS‡ HP = 226 ± 22 J K −1 mol −1 for the k HP path, [Formula: see text] and [Formula: see text] for the k H 2 P path and [Formula: see text] and [Formula: see text] for the k H 3 P path. The kinetic results show the high reactivity of mercury(II) hydroxide towards the protonated porphyrin.

show abstract

Kinetics and mechanisms of metalloporphyrin reactions

Cited by 120 publications

References 185 publications

Solvent effect on protonation of tpps in water-DMF mixtures

Solvent effect on protonation of tpps in water-DMF mixtures

Kinetics and mechanisms of the formation of a sitting-atop complex of N-alkylporphyrin with Al(III) in moist acetonitrile

Kinetics and Mechanism of the Reaction of Mercury(II) with a Water-soluble Octabromoporphyrin

Contact Info

Product

Resources

About