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The acid properties of benzodiamyloxyl and thiadiazole porphyrazine derivatives in the H2L-(K[2.2.2])OH-DMSO system

  • Physical Chemistry of Solutions
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Abstract

Step acid dissociation reactions of benzodiamyloxyl (X) and thiadiazole (Y) porphyrazine (H2PA) derivatives H2PA(X)4, H2PA(X)3(Y), H2PA(X)2(Y)2, H2PA(X)(Y)3, and H2PA(Y)4 were studied theoretically (MP3) and experimentally (spectropotentiometrically) in the H2L-(K[2.2.2])OH-DMSO system for the series H2P (porphin), H2P(μs-Pr)4, H2P(μs-Ph)4, H(N-Me)P(μs-Ph)4, H2TBP (tetrabenzoporphin), H2TBP(μs-Ph)4, H2PA (porphyrazine), H2PA(β-Ph)4, H2PC (phthalocyanine), and H2PC(t-Bt)4. The linear correlation pK 298a1 = 0.32622ΔH° a1(g) − 94.62 (R = 0.998) was observed for H2PA and its symmetrical derivatives H2PA(β-Ph)4, H2PC, H2PC(t-Bt)4, H2PC(X)4, and H2PC(Y)4. Deviations of the proportionality factors in the pK 298a1 = bH° a1(g) + A dependences from the theoretical value (2.303RT)−1 were explained by medium effects. Substituent effects on pK 298a1 were divided into internal δ(R i)int and external δ(R i)ext (solvation) contributions. The compensation dependences δ(R i)ext = −0.10911δ(R i)int + 0.13 and δ(R i)ext = −0.52969δ(R i)int (correlation coefficients 0.998) were observed for simple (H2PA, H2TBP, H2P(μs-Ph)4, and H2P(μs-Pr)4) and complex (H(N-Me)P(Ph)4, H2TBP(μs-Ph)4, H2PA(β-Ph)4,H2PA(Y)4, H2PC, H2PC(t-Bt)4, and H2PC(X)4) porphin derivatives, respectively.

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Authors and Affiliations

  1. Institute of the Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia

    V. B. Sheinin & Yu. B. Ivanova

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  1. V. B. Sheinin
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  2. Yu. B. Ivanova
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Original Russian Text © V.B. Sheinin, Yu.B. Ivanova, 2007, published in Zhurnal Fizicheskoi Khimii, 2007, Vol. 81, No. 8, pp. 1419–1424.

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Sheinin, V.B., Ivanova, Y.B. The acid properties of benzodiamyloxyl and thiadiazole porphyrazine derivatives in the H2L-(K[2.2.2])OH-DMSO system. Russ. J. Phys. Chem. 81, 1250–1255 (2007). https://doi.org/10.1134/S0036024407080134

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  • DOI: https://doi.org/10.1134/S0036024407080134

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