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- W2020849992 abstract "The rate constant of the four-site cyclic chemical exchange between pyrrole protons in tetramesitylporphyrinatoiron(III)bis(2-methylimidazole) has been measured in the temperature range 236−255 K from 1H transverse relaxation times (T2) observed at the 500 MHz field strength. The values of the rate constant were obtained through the simulation of the observed T2's under the assumption that their values are dominated by the rate of the chemical exchange. The measurement of the exchange rate constant was also attempted at a lower temperature (230 K), but the use of extrapolated intrinsic T2's at that temperature introduces a significant error into the simulated rate constant. The thermodynamic activation parameters of the cyclic exchange were determined as ΔH⧧ = 48 ± 1 kJ/mol and ΔS⧧ = −10 ± 6 J/K·mol. The value of k varied from 30 to 270 s-1 in the temperature range 236−255 K. The near-zero exchange activation entropy is consistent with two previous studies but contradicts another study based on saturation..." @default.
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- W2020849992 date "1998-12-01" @default.
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- W2020849992 title "Rate Constants and Thermodynamic Parameters of Rotation of Axial Ligands in a Bisligated Ferric Tetramesitylporphyrinate Complex Measured from the Temperature Dependence of1H Transverse Relaxation Rates" @default.
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